U.S. patent application number 10/829572 was filed with the patent office on 2005-02-03 for herbicidal compositions containing glyphosate and a pyridine analog.
This patent application is currently assigned to Monsanto Technology LLC. Invention is credited to Ratliff, Paul G., Sandbrink, Joseph J., Wright, Daniel R..
Application Number | 20050026781 10/829572 |
Document ID | / |
Family ID | 34108873 |
Filed Date | 2005-02-03 |
United States Patent
Application |
20050026781 |
Kind Code |
A1 |
Wright, Daniel R. ; et
al. |
February 3, 2005 |
Herbicidal compositions containing glyphosate and a pyridine
analog
Abstract
The present invention is directed to herbicidal compositions or
formulations, and to methods of using such compositions or
formulations to kill, or control the growth and proliferation of,
unwanted plants. In particular, the present invention is directed
to herbicidal compositions or formulations, as well as their
methods of use, which comprise N-phosphonomethylglycine or a
herbicidal derivative thereof, a pyridine analog or a herbicidal
derivative thereof, and optionally one or more suitable
surfactants, with N-phosphonomethylglycine being in excess relative
to the pyridine analog. Such compositions cause early visual
symptoms of treatment and/or enhanced effectiveness or control when
applied to the foliage of plants.
Inventors: |
Wright, Daniel R.; (St.
Louis, MO) ; Sandbrink, Joseph J.; (St. Louis,
MO) ; Ratliff, Paul G.; (Olivette, MO) |
Correspondence
Address: |
SENNIGER POWERS LEAVITT AND ROEDEL
ONE METROPOLITAN SQUARE
16TH FLOOR
ST LOUIS
MO
63102
US
|
Assignee: |
Monsanto Technology LLC
|
Family ID: |
34108873 |
Appl. No.: |
10/829572 |
Filed: |
April 22, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60496031 |
Apr 22, 2003 |
|
|
|
60552065 |
Mar 10, 2004 |
|
|
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Current U.S.
Class: |
504/128 |
Current CPC
Class: |
A01N 57/02 20130101;
A01N 57/20 20130101; A01N 57/20 20130101; A01N 43/40 20130101; A01N
2300/00 20130101; A01N 25/30 20130101; A01N 43/78 20130101; A01N
43/40 20130101; A01N 57/20 20130101 |
Class at
Publication: |
504/128 |
International
Class: |
A01N 057/00; A01N
025/00 |
Claims
What is claimed is:
1. An aqueous herbicidal liquid concentrate which may be diluted
with water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant, the concentrate comprising:
glyphosate or a herbicidal derivative thereof in a concentration of
at least about 50 grams acid equivalent per liter; a pyridine
analog selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof; and, at least one surfactant; wherein (i) the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 1.7:1, and (ii)
when the glyphosate is predominantly in the form of a salt, said
salt is selected from the group consisting of a sodium salt, an
ammonium salt, an alkylammonium salt, a C.sub.3-C16 alkanolammonium
salt, a di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
2. The aqueous herbicidal liquid concentrate of claim 1 wherein the
glyphosate concentration ranges from at least about 100 grams to
about 400 grams acid equivalent per liter.
3. The aqueous herbicidal liquid concentrate of claim 1 wherein the
pyridine analog concentration ranges from at least about 8 to about
20 grams acid equivalent per liter.
4. The aqueous herbicidal liquid concentrate of claim 1 wherein the
weight ratio (a.e. basis) of glyphosate to pyridine analog is at
least about 8:1.
5. The aqueous herbicidal liquid concentrate of claim 1 wherein the
weight ratio (a.e. basis) of glyphosate to pyridine analog ranges
from about 8:1 to about 20:1.
6. An aqueous herbicidal liquid concentrate which may be diluted
with water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant, the concentrate comprising:
glyphosate or a herbicidal derivative thereof; a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof; and, at least one surfactant in a concentration ranging
from about 1 grams to 283 grams per liter; wherein (i) the
glyphosate (acid equivalent basis) and the pyridine analog (acid
equivalent basis) are present in a weight ratio of at least 1:1,
glyphosate being in excess, and (ii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-C.sub.16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
7. The aqueous herbicidal liquid concentrate of claim 6 wherein the
glyphosate concentration ranges from at least about 100 grams to
about 400 grams acid equivalent per liter.
8. The aqueous herbicidal liquid concentrate of claim 6 wherein the
pyridine analog concentration ranges from at least about 8 to about
20 grams acid equivalent per liter.
9. The aqueous herbicidal liquid concentrate of claim 6 wherein the
weight ratio (a.e. basis) of glyphosate to pyridine analog is at
least about 8:1.
10. The aqueous herbicidal liquid concentrate of claim 6 wherein
the weight ratio (a.e. basis) of glyphosate to pyridine analog
ranges from about 8:1 to about 20:1.
11. An aqueous herbicidal liquid concentrate which may be diluted
with water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant, the concentrate comprising:
glyphosate or a herbicidal derivative thereof; a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, in a concentration ranging from about 1 gram to 99 grams
(acid equivalent basis) per liter; and, at least one surfactant;
wherein (i) the glyphosate (acid equivalent basis) and the pyridine
analog (acid equivalent basis) are present in a weight ratio of at
least 1:1, glyphosate being in excess, and (ii) when the glyphosate
is predominantly in the form of a salt, said salt is selected from
the group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-C.sub.16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
12. The aqueous herbicidal liquid concentrate of claim 11 wherein
the glyphosate concentration ranges from at least about 100 grams
to about 400 grams acid equivalent per liter.
13. The aqueous herbicidal liquid concentrate of claim 11 wherein
the pyridine analog concentration ranges from at least about 8
grams to about 20 grams acid equivalent per liter.
14. The aqueous herbicidal liquid concentrate of claim 11 wherein
the weight ratio (a.e. basis) of glyphosate to pyridine analog is
at least about 8:1.
15. The aqueous herbicidal liquid concentrate of claim 11 wherein
the weight ratio (a.e. basis) of glyphosate to pyridine analog
ranges from about 8:1 to about 20:1.
16. An aqueous herbicidal liquid concentrate which may be diluted
with water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant, the concentrate comprising:
glyphosate or a herbicidal derivative thereof; a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof; and, at least one surfactant; wherein (i) the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 1:1, (ii) the
glyphosate (acid equivalent basis) and the surfactant are present
in a weight ratio of at least 1:1, wherein glyphosate is in excess
in both instances, and (iii) when the glyphosate is predominantly
in the form of a salt, said salt is selected from the group
consisting of a sodium salt, an ammonium salt, an alkylammonium
salt, a C.sub.3-C.sub.16 alkanolammonium salt, a di-ammonium salt,
an alkylamine salt, a C.sub.3-C.sub.16 alkanolamine salt, an
alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
17. The aqueous herbicidal liquid concentrate of claim 16 wherein
the glyphosate concentration ranges from at least about 100 grams
to about 400 grams acid equivalent per liter.
18. The aqueous herbicidal liquid concentrate of claim 16 wherein
the pyridine analog concentration ranges from at least about 8 to
about 20 grams acid equivalent per liter.
19. The aqueous herbicidal liquid concentrate of claim 16 wherein
the weight ratio (a.e. basis) of glyphosate to pyridine analog is
at least about 8:1.
20. The aqueous herbicidal liquid concentrate of claim 16 wherein
the weight ratio (a.e. basis) of glyphosate to pyridine analog
ranges from about 8:1 to about 20:1.
21. An aqueous herbicidal liquid concentrate which may be diluted
with water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant, the concentrate comprising:
glyphosate or a herbicidal derivative thereof; and, a pyridine
analog selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof; wherein the glyphosate (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 1:1, glyphosate being in excess, and further
wherein (i) the pyridine analog or a herbicidal derivative thereof
is present at a concentration of not greater than 99 grams (acid
equivalent) per liter, and (ii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-C.sub.16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
22. An aqueous herbicidal liquid concentrate which may be diluted
with water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant, the concentrate comprising:
glyphosate or a herbicidal derivative thereof; and, a pyridine
analog, or a herbicidal derivative thereof; wherein the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 1:1, glyphosate
being in excess, and further wherein (i) the glyphosate (acid
equivalent basis) or herbicidal derivative thereof is present at a
concentration of not greater than 165 grams (acid equivalent) per
liter, and (ii) when the glyphosate is predominantly in the form of
a salt, said salt is selected from the group consisting of a sodium
salt, an ammonium salt, an alkylammonium salt, a C.sub.3-C.sub.16
alkanolammonium salt, a di-ammonium salt, an alkylamine salt, a
C.sub.3-C.sub.16 alkanolamine salt, an alkylsulfonium salt, a
sulfoxonium salt, and combinations thereof.
23. The aqueous herbicidal liquid concentrate of claim 21 or 22
wherein said concentrate further comprises a surfactant.
24. The aqueous herbicidal liquid concentrate of claim 21 or 22
wherein the glyphosate concentration ranges from at least about 75
grams to about 160 grams acid equivalent per liter.
25. The aqueous herbicidal liquid concentrate of claim 21 or 22
wherein the pyridine analog concentration ranges from at least
about 8 to about 20 grams acid equivalent per liter.
26. The aqueous herbicidal liquid concentrate of claim 21 or 22
wherein the weight ratio (a.e. basis) of glyphosate to pyridine
analog ranges from about 8:1 to about 20:1.
27. An aqueous herbicidal liquid concentrate which may be diluted
with water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant, the concentrate comprising:
at least one glyphosate salt predominantly in the form of potassium
glyphosate, monoethanolamine glyphosate, or a mixture thereof; a
pyridine analog selected from the group consisting of triclopyr,
clopyralid, fluroxypyr, dithiopyr, thiazopyr and picloram, or a
herbicidal derivative thereof; and, at least one surfactant in a
concentration less than 20 grams per liter; wherein the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 1:1, glyphosate
being in excess.
28. The aqueous herbicidal liquid concentrate of one of preceding
claims 1, 6, 11, 16, 21, 22 or 27 wherein said surfactant is
selected from the group consisting of: (a) a secondary or tertiary
amine having the formula: 19wherein R.sup.1 and R.sup.2 are
hydrocarbyl having from 1 to about 30 carbon atoms, and R.sup.3 is
hydrogen or hydrocarbyl having from 1 to about 30 carbon atoms; (b)
a monoalkoxylated amine having the formula: 20wherein R.sup.1 and
R.sup.4 are independently hydrocarbyl or substituted hydrocarbyl
groups having from 1 to about 30 carbon atoms or --R.sup.5SR.sup.6,
R.sup.2 in each of the x (R.sup.2O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a linear or
branched alkyl group having from 1 to about 4 carbon atoms, R.sup.5
is a linear or branched alkyl group having from about 6 to about 30
carbon atoms, R.sup.6 is a hydrocarbyl or substituted hydrocarbyl
group having from 4 to about 15 carbon atoms and x is an average
number from 1 to about 60; (c) a dialkoxylated quaternary ammonium
salt having the formula: 21wherein R.sup.1 is hydrocarbyl or
substituted hydrocarbyl having from 1 to about 30 carbon atoms,
R.sup.2 in each of the x (R.sup.2O) and y (R.sup.2O) groups is
independently C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a
linear or branched alkyl group having from 1 to about 4 carbon
atoms, R.sup.4 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, x and y are
independently an average number from 1 to about 40, and X- is an
agriculturally acceptable anion; (d) a monoalkoxylated quaternary
ammonium salt having the formula: 22wherein R.sup.1 and R.sup.5 are
independently hydrogen or hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, R.sup.4 is hydrocarbyl or
substituted hydrocarbyl having from 1 to about 30 carbon atoms,
R.sup.2 in each of the x (R.sup.2O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a linear or
branched alkyl group having from 1 to about 30 carbon atoms, x is
an average number from 1 to about 60, and X- is an agriculturally
acceptable anion; (e) a quaternary ammonium salt having the
formula: 23wherein R.sup.1, R.sup.3 and R.sup.4 are independently
hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to
about 30 carbon atoms, R.sup.2 is hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, and X- is an
agriculturally acceptable anion; (f) an ether amines having the
formula: 24wherein R.sup.1 is hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; R.sup.2 is
hydrocarbylene or substituted hydrocarbylene having from 2 to about
30 carbon atoms; R.sup.3 and R.sup.4 are independently hydrogen,
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, or --(R.sup.5O).sub.xR.sup.6, R.sup.5 in each of the
x(R.sup.5--O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.6 is hydrogen, or a linear or branched alkyl group having
from 1 to about 4 carbon atoms, and x is an average number from 1
to about 50; (g) a diamine having the formula: 25wherein R.sup.1,
R.sup.3, R.sup.4 and R.sup.5 are independently hydrogen,
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, or --(R.sup.6O).sub.xR.sup.7; R.sup.2 and R.sup.8 are
independently hydrocarbylene or substituted hydrocarbylene having
from 2 to about 30 carbon atoms, R.sup.6 in each of the x
(R.sup.6O) and y (R.sup.6O) groups is independently C.sub.2-C.sub.4
alkylene, R.sup.7 is hydrogen, or a linear or branched alkyl group
having from 1 to about 30 carbon atoms, x is an average number from
1 to about 30, X is --O--, --N(R.sup.6)--, --C(O)--, --C(O)O--,
--OC(O)--, --N(R.sup.9)C(O)--, --C(O)N(R.sup.9)--, --S--, --SO--,
or --SO.sub.2--, y is 0 or an average number from 1 to about 30, n
and z are independently 0 or 1, and R.sup.9 is hydrogen or
hydrocarbyl or substituted hydrocarbyl; (h) an amine oxide having
the formula: 26wherein R.sup.1, R.sup.2 and R.sup.3 are
independently hydrogen, hydrocarbyl or substituted hydrocarbyl,
--(R.sup.4O).sub.xR.sup.5, or --R.sup.6(OR.sup.4).sub.xOR.sup.5;
R.sup.4 in each of the x (R.sup.4O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.5 is hydrogen, or a linear or
branched alkyl group having from 1 to about 30 carbon atoms,
R.sup.6 is hydrocarbylene or substituted hydrocarbylene having from
2 to about 6 carbon atoms, x is an average number from 1 to about
50, and the total number of carbon atoms in R.sup.1, R.sup.2 and
R.sup.3 is at least 8; (i) a dialkoxylated amine having the
formula: 27wherein R.sup.1 is a hydrocarbyl or substituted
hydrocarbyl having from about 6 to about 30 carbon atoms, or
--R.sup.4SR.sup.5, R.sup.4 and R.sup.2 in each of the x (R.sup.2O)
and the y (R.sup.2O) groups is independently C.sub.2-C.sub.4
alkylene, R.sup.3 is hydrogen, or a linear or branched alkyl group
having from 1 to about 4 carbon atoms, R.sup.5 is a linear or
branched alkyl group having from about 4 to about 15 carbon atoms,
and x and y are independently an average number from 1 to about 40;
(j) an aminated alkoxylated alcohol having the structure: 28wherein
R.sup.1, R.sup.7, R.sup.8, and R.sup.9 are each independently
hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to
about 30 carbon atoms, or --(R.sup.11).sub.s(R.sup.3O).s-
ub.vR.sup.10; X is --O--, --OC(O)--, --C(O)O--,
--N(R.sup.12)C(O)--, --C(O)N(R.sup.12)--, --S--, --SO--,
--SO.sub.2-- or --N(R.sup.9)--; R.sup.3 in each of the n (R.sup.3O)
groups and the v (R.sup.3O) groups is independently C.sub.2-C.sub.4
alkylene; R.sup.10 is hydrogen, or a linear or branched alkyl group
having from 1 to about 30 carbon atoms; n is an average number from
1 to about 60; v is an average number from 1 to about 50; R.sup.2
and R.sup.11 are each independently hydrocarbylene or substituted
hydrocarbylene having from 1 to about 6 carbon atoms; R.sup.4 is
hydrocarbylene or substituted hydrocarbylene having from 2 to about
6 carbon atoms; R.sup.12 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; m and s are
each independently 0 or 1; R.sup.6 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 30 carbon atoms,
--C(.dbd.NR.sup.12)--, --C(S)--, or --C(O)--; q is an integer from
0 to 5; and R.sup.5 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; (k) a
quaternary ammonium, sulfonium and sulfoxonium salt having the
formula: 29wherein R.sup.1, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and
R.sup.11 are independently hydrogen, hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, or
--(R.sup.13).sub.s(R.sup.3O).sub.vR.sup.12; X is --O--, --OC(O)--,
--N(R.sup.14)C(O)--, --C(O)N(R.sup.14)--, --C(O)O--, or --S--;
R.sup.3 in each of the n (R.sup.3O) groups and v (R.sup.3O) groups
is independently C.sub.2-C.sub.4 alkylene; R.sup.12 is hydrogen, or
a linear or branched alkyl group having from 1 to about 30 carbon
atoms; n is an average number from 1 to about 60; v is an average
number from 1 to about 50; R.sup.2 and R.sup.13 are each
independently hydrocarbylene or substituted hydrocarbylene having
from 1 to about 6 carbon atoms; m and s are each independently 0 or
1; R.sup.4 is hydrocarbylene or substituted hydrocarbylene having
from 2 to about 6 carbon atoms; R.sup.6 is hydrocarbylene or
substituted hydrocarbylene having from 2 to about 30 carbon atoms,
--C(.dbd.NR.sup.12)--, --C(S)--, or --C(O)--; R.sup.14 is hydrogen
or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, q is an integer from 0 to 5; R.sup.5 is hydrogen or
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms; and each A.sup.- is an agriculturally acceptable
anion; (l) a diamine or diammonium salt having the formula:
30wherein R.sup.1, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8
are independently hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, R.sup.2 in each
of the m (R.sup.2O) and n (R.sup.2O) groups and R.sup.9 are
independently C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrocarbylene
or substituted hydrocarbylene having from about 2 to about 6 carbon
atoms or --(R.sup.2O).sub.pR.sub.9--, m and n are individually an
average number from 0 to about 50, and p is an average number from
0 to about 60; (m) an alkoxylated alcohol having the
formula:R.sup.1O--(R.sup.2O).sub.xR.sup.3 (18)wherein R.sup.1 is
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, R.sup.2 in each of the x (R.sup.2O) groups is
independently C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a
linear or branched alkyl group having from 1 to about 4 carbon
atoms, and x is an average number from 1 to about 60; (n) an
alkoxylated dialkylphenol having the formula: 31wherein R.sup.1 and
R.sup.4 are independently hydrogen, or a linear or branched alkyl
group having from 1 to about 30 carbon atoms and at least one of
R.sup.1 and R.sup.4 is an alkyl group, R.sup.2 in each of the x
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, or a linear or branched alkyl group having
from 1 to about 4 carbon atoms, and x is an average number from 1
to about 60; (o) an alkyl alkoxylated phosphate having the formula:
32wherein R.sup.1 and R.sup.3 are independently a linear or
branched alkyl, linear or branched alkenyl, linear or branched
alkynyl, aryl, or aralkyl group having from about 4 to about 30
carbon atoms; R.sup.2 in each of the m (R.sup.2O) and the n
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene; and m
and n are independently from 1 to about 30; (p) an alkyl
alkoxylated phosphate having the formula: 33wherein R.sup.1 is a
linear or branched alkyl, linear or branched alkenyl, linear or
branched alkynyl, aryl, or aralkyl group having from about 8 to
about 30 carbon atoms; R.sup.2 in each of the m (R.sup.2O) groups
is independently C.sub.2-C.sub.4 alkylene; and m is from 1 to about
30; and mixtures or combinations thereof.
29. An aqueous herbicidal composition useful for killing or
controlling the growth of unwanted plants comprising: glyphosate or
a herbicidal derivative thereof; pyridine analog or a herbicidal
derivative thereof; and, at least one surfactant; wherein the
glyphosate (acid equivalent basis) and the pyridine analog (acid
equivalent basis) are present in a weight ratio of at least 7.6:1,
and further wherein when the glyphosate is predominantly in the
form of a salt, said salt is selected from the group consisting of
a sodium salt, an ammonium salt, an alkylammonium salt, a
C.sub.3-C.sub.16 alkanolammonium salt, a di-ammonium salt, an
alkylamine salt, a C.sub.3-C.sub.16 alkanolamine salt, an
alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
30. The aqueous herbicidal composition of claim 29 wherein the
glyphosate concentration ranges from about 4 grams to about 25
grams acid equivalent per liter.
31. The aqueous herbicidal composition of claim 29 wherein the
pyridine analog concentration ranges from about 0.4 grams to about
6 grams acid equivalent per liter.
32. The aqueous herbicidal composition of claim 29 wherein the
weight ratio (a.e. basis) of glyphosate to pyridine analog ranges
from about 8:1 to about 15:1.
33. An aqueous herbicidal composition useful for killing or
controlling the growth of unwanted plants comprising: glyphosate or
a herbicidal derivative thereof; a pyridine analog selected from
the group consisting of triclopyr, clopyralid, dithiopyr, thiazopyr
and picloram, or a herbicidal derivative thereof, in a
concentration of not greater than 3.9 grams (acid equivalent basis)
per liter; and, at least one surfactant; wherein (i) the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least about 1:1,
glyphosate being in excess, and (ii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-C.sub.16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
34. The aqueous herbicidal composition of claim 33 wherein the
glyphosate concentration ranges from about 4 grams to about 25
grams acid equivalent per liter.
35. The aqueous herbicidal composition of claim 33 wherein the
pyridine analog concentration ranges from about 0.4 grams to about
3 grams acid equivalent per liter.
36. The aqueous herbicidal composition of claim 33 wherein the
weight ratio (a.e. basis) of glyphosate to pyridine analog ranges
from about 8:1 to about 20:1.
37. An aqueous herbicidal composition useful for killing or
controlling the growth of unwanted plants comprising: glyphosate,
or a herbicidal derivative thereof; a pyridine analog selected from
the group consisting of triclopyr, clopyralid, dithiopyr, thiazopyr
and picloram, or a herbicidal derivative thereof; and, at least one
surfactant; wherein (i) the surfactant concentration is not greater
than 3.9 grams per liter, (ii) glyphosate (acid equivalent basis)
and the pyridine analog (acid equivalent basis) are present in a
weight ratio of at least 3:1, and (iii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-C.sub.16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
38. An aqueous herbicidal composition useful for killing or
controlling the growth of unwanted plants comprising: glyphosate,
or a herbicidal derivative thereof; a pyridine analog, or a
herbicidal derivative thereof; and, at least one surfactant;
wherein (i) the surfactant concentration is not greater than 6.6
grams per liter, (ii) glyphosate (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 5:1, and (iii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-C.sub.16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
39. An aqueous herbicidal composition useful for killing or
controlling the growth of unwanted plants comprising: glyphosate,
or a herbicidal derivative thereof; a pyridine analog, or a
herbicidal derivative thereof; and, at least one surfactant;
wherein (i) the surfactant concentration is not greater than 9.3
grams per liter, (ii) glyphosate (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 7:1, and (iii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-C.sub.16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
40. The aqueous herbicidal composition of one of claims 37, 38 or
39 wherein the glyphosate concentration ranges from about 4 grams
to about 25 grams acid equivalent per liter.
41. The aqueous herbicidal composition of one of claims 37, 38 or
39 wherein the pyridine analog concentration ranges from about 0.4
grams to about 6 grams acid equivalent per liter.
42. An aqueous herbicidal composition useful for killing or
controlling the growth of unwanted plants comprising: glyphosate or
a herbicidal derivative thereof; pyridine analog or a herbicidal
derivative thereof; and, at least one surfactant; wherein either
(i) the glyphosate concentration (acid equivalent basis) is not
greater than 16.2 grams per liter, and the glyphosate (acid
equivalent basis) and pyridine analog (acid equivalent basis) are
present in a weight ratio of at least 4:1; or (ii) the glyphosate
concentration (acid equivalent basis) is not greater than 23.8
grams per liter, and the glyphosate (acid equivalent basis) and
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 6:1; and further wherein when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-C.sub.16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-C.sub.16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
43. The aqueous herbicidal composition of claim 42 wherein the
glyphosate concentration is not greater than about 15 grams acid
equivalent per liter and the weight ratio (a.e. to a.e.) of
glyphosate to pyridine analog is at least about 10:1.
44. The aqueous herbicidal composition of claim 42 wherein the
glyphosate concentration is not greater than about 20 grams acid
equivalent per liter and the weight ratio (a.e. to a.e.) of
glyphosate to pyridine analog is at least about 10:1.
45. The aqueous herbicidal composition of claim 42 wherein the
pyridine analog concentration ranges from about 0.4 grams to about
6 grams acid equivalent per liter.
46. An aqueous herbicidal composition useful for killing or
controlling the growth of unwanted plants comprising: at least one
glyphosate salt predominantly in the form of potassium glyphosate,
monoethanolamine glyphosate, or a mixture thereof; and a pyridine
analog selected from the group consisting of triclopyr, clopyralid,
fluroxypyr, dithiopyr, thiazopyr and picloram, or a herbicidal
derivative thereof; wherein (i) the glyphosate salt is present in a
concentration less than 180 grams acid equivalent per liter and the
glyphosate salt (acid equivalent basis) and the pyridine analog
(acid equivalent basis) are present in a weight ratio of at least
1:1, glyphosate being in excess; (ii) the glyphosate salt is
present in a concentration less than 240 grams acid equivalent per
liter and the glyphosate salt (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 2:1; (iii) the glyphosate salt is present in a
concentration less than 270 grams acid equivalent per liter and the
glyphosate salt (acid equivalent basis) and the pyridine analog
(acid equivalent basis) are present in a weight ratio of at least
3:1; (iv) the glyphosate salt is present in a concentration less
than 288 grams acid equivalent per liter and the glyphosate salt
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 4:1; (v) the
glyphosate salt is present in a concentration less than 300 grams
acid equivalent per liter and the glyphosate salt (acid equivalent
basis) and the pyridine analog (acid equivalent basis) are present
in a weight ratio of at least 5:1; (vi) the glyphosate salt is
present in a concentration less than 308 grams acid equivalent per
liter and the glyphosate salt (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 6:1; (vii) the glyphosate salt is present in a
concentration less than 315 grams acid equivalent per liter and the
glyphosate salt (acid equivalent basis) and the pyridine analog
(acid equivalent basis) are present in a weight ratio of at least
7:1; (viii) the glyphosate salt is present in a concentration less
than 320 grams acid equivalent per liter and the glyphosate salt
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 8:1; (ix) the
glyphosate salt is present in a concentration less than 324 grams
acid equivalent per liter and the glyphosate salt (acid equivalent
basis) and the pyridine analog (acid equivalent basis) are present
in a weight ratio of at least 9:1; or (x) the glyphosate salt is
present in a concentration less than 326 grams acid equivalent per
liter and the glyphosate salt (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 10:1.
47. The aqueous herbicidal composition of claim 46 wherein the
glyphosate concentration ranges from about 4 grams to about 25
grams acid equivalent per liter.
48. The aqueous herbicidal composition of claim 46 wherein the
pyridine analog concentration ranges from about 0.8 grams to about
2 grams acid equivalent per liter.
49. The aqueous herbicidal composition of claim 46 wherein the
weight ratio (a.e. basis) of glyphosate to pyridine analog is at
least about 11:1.
50. The aqueous herbicidal composition of claim 46 wherein the
weight ratio (a.e. basis) of glyphosate to pyridine analog is at
least about 15:1.
51. The aqueous herbicidal composition of claim 46 further
comprising a surfactant.
52. The aqueous herbicidal composition of claim 51 wherein the
composition is a liquid concentrate which may be diluted with water
to provide an aqueous herbicidal application mixture for
application to the foliage of a plant.
53. The aqueous herbicidal composition of one of preceding claims
29, 33, 37, 38, 39, 42 or 51 wherein said surfactant is selected
from the group consisting of: (a) a secondary or tertiary amine
having the formula: 34wherein R.sup.1 and R.sup.2 are hydrocarbyl
having from 1 to about 30 carbon atoms, and R.sup.3 is hydrogen or
hydrocarbyl having from 1 to about 30 carbon atoms; (b) a
monoalkoxylated amine having the formula: 35wherein R.sup.1 and
R.sup.4 are independently hydrocarbyl or substituted hydrocarbyl
groups having from 1 to about 30 carbon atoms or --R.sup.5SR.sup.6,
R.sup.2 in each of the x (R.sup.2O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a linear or
branched alkyl group having from 1 to about 4 carbon atoms, R.sup.5
is a linear or branched alkyl group having from about 6 to about 30
carbon atoms, R.sup.6 is a hydrocarbyl or substituted hydrocarbyl
group having from 4 to about 15 carbon atoms and x is an average
number from 1 to about 60; (c) a dialkoxylated quaternary ammonium
salt having the formula: 36wherein R.sup.1 is hydrocarbyl or
substituted hydrocarbyl having from 1 to about 30 carbon atoms,
R.sup.2 in each of the x (R.sup.2O) and y (R.sup.2O) groups is
independently C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a
linear or branched alkyl group having from 1 to about 4 carbon
atoms, R.sup.4 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, x and y are
independently an average number from 1 to about 40, and X- is an
agriculturally acceptable anion; (d) a monoalkoxylated quaternary
ammonium salt having the formula: 37wherein R.sup.1 and R.sup.5 are
independently hydrogen or hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, R.sup.4 is hydrocarbyl or
substituted hydrocarbyl having from 1 to about 30 carbon atoms,
R.sup.2 in each of the x (R.sup.2O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a linear or
branched alkyl group having from 1 to about 30 carbon atoms, x is
an average number from 1 to about 60, and X- is an agriculturally
acceptable anion; (e) a quaternary ammonium salt having the
formula: 38wherein R.sup.1, R.sup.3 and R.sup.4 are independently
hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to
about 30 carbon atoms, R.sup.2 is hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, and X- is an
agriculturally acceptable anion; (f) an ether amine having the
formula: 39wherein R.sup.1 is hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; R.sup.2 is
hydrocarbylene or substituted hydrocarbylene having from 2 to about
30 carbon atoms; R.sup.3 and R.sup.4 are independently hydrogen,
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, or --(R.sup.5O).sub.xR.sup.6, R.sup.5 in each of the
x(R.sup.5--O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.6 is hydrogen, or a linear or branched alkyl group having
from 1 to about 4 carbon atoms, and x is an average number from 1
to about 50; (g) a diamine having the formula: 40wherein R.sup.1,
R.sup.3, R.sup.4 and R.sup.5 are independently hydrogen,
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, or --(R.sup.6O).sub.xR.sup.7; R.sup.2 and R.sup.8 are
independently hydrocarbylene or substituted hydrocarbylene having
from 2 to about 30 carbon atoms, R.sup.6 in each of the x
(R.sup.6O) and y (R.sup.6O) groups is independently C.sub.2-C.sub.4
alkylene, R.sup.7 is hydrogen, or a linear or branched alkyl group
having from 1 to about 30 carbon atoms, x is an average number from
1 to about 30, X is --O--, --N(R.sup.6)--, --C(O)--, --C(O)O--,
--OC(O)--, --N(R.sup.9)C(O)--, --C(O)N(R.sup.9)--, --S--, --SO--,
or --SO.sub.2--, y is 0 or an average number from 1 to about 30, n
and z are independently 0 or 1, and R.sup.9 is hydrogen or
hydrocarbyl or substituted hydrocarbyl; (h) an amine oxide having
the formula: 41wherein R.sup.1, R.sup.2 and R.sup.3 are
independently hydrogen, hydrocarbyl or substituted hydrocarbyl,
--(R.sup.4O).sub.xR.sup.5, or --R.sup.6(OR.sup.4).sub.xOR.sup.5;
R.sup.4 in each of the x (R.sup.4O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.5 is hydrogen, or a linear or
branched alkyl group having from 1 to about 30 carbon atoms,
R.sup.6 is hydrocarbylene or substituted hydrocarbylene having from
2 to about 6 carbon atoms, x is an average number from 1 to about
50, and the total number of carbon atoms in R.sup.1, R.sup.2 and
R.sup.3 is at least 8; (i) a dialkoxylated amine having the
formula: 42wherein R.sup.1 is a hydrocarbyl or substituted
hydrocarbyl having from about 6 to about 30 carbon atoms, or
--R.sup.4SR.sup.5, R.sup.4 and R.sup.2 in each of the x (R.sup.2O)
and the y (R.sup.2O) groups is independently C.sub.2-C.sub.4
alkylene, R.sup.3 is hydrogen, or a linear or branched alkyl group
having from 1 to about 4 carbon atoms, R.sup.5 is a linear or
branched alkyl group having from about 4 to about 15 carbon atoms,
and x and y are independently an average number from 1 to about 40;
(j) an aminated alkoxylated alcohol having the structure: 43wherein
R.sup.1, R.sup.7, R.sup.8, and R.sup.9are each independently
hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to
about 30 carbon atoms, or
--(R.sup.11).sub.s(R.sup.3O).sub.vR.sup.10; X is --O--, --OC(O)--,
--C(O)O--, --N(R.sup.12)C(O)--, --C(O)N(R.sup.12)--, --S--, --SO--,
--SO.sub.2-- or --N(R.sup.9)--; R.sup.3 in each of the n (R.sup.3O)
groups and the v (R.sup.3O) groups is independently C.sub.2-C.sub.4
alkylene; R.sup.10 is hydrogen, or a linear or branched alkyl group
having from 1 to about 30 carbon atoms; n is an average number from
1 to about 60; v is an average number from 1 to about 50; R.sup.2
and R.sup.11 are each independently hydrocarbylene or substituted
hydrocarbylene having from 1 to about 6 carbon atoms; R.sup.4 is
hydrocarbylene or substituted hydrocarbylene having from 2 to about
6 carbon atoms; R.sup.12 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; m and s are
each independently 0 or 1; R.sup.6 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 30 carbon atoms,
--C(.dbd.NR.sup.12)--, --C(S)--, or --C(O)--; q is an integer from
0 to 5; and R.sup.5 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; (k) a
quaternary ammonium, sulfonium or sulfoxonium salt having the
formula: 44wherein R.sup.1, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and
R.sup.11 are independently hydrogen, hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, or
--(R.sup.13).sub.s(R.sup.3O).sub.vR.s- up.12; X is --O--,
--OC(O)--, --N(R.sup.14)C(O)--, --C(O)N(R.sup.14)--, --C(O)O--, or
--S--; R.sup.3 in each of the n (R.sup.3O) groups and v (R.sup.3O)
groups is independently C.sub.2-C.sub.4 alkylene; R.sup.12 is
hydrogen, or a linear or branched alkyl group having from 1 to
about 30 carbon atoms; n is an average number from 1 to about 60; v
is an average number from 1 to about 50; R.sup.2 and R.sup.13 are
each independently hydrocarbylene or substituted hydrocarbylene
having from 1 to about 6 carbon atoms; m and s are each
independently 0 or 1; R.sup.4 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 6 carbon atoms; R.sup.6 is
hydrocarbylene or substituted hydrocarbylene having from 2 to about
30 carbon atoms, --C(.dbd.NR.sup.12)--, --C(S)--, or --C(O)--;
R.sup.14 is hydrogen or hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, q is an integer from 0 to
5; R.sup.5 is hydrogen or hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms; and each A.sup.- is an
agriculturally acceptable anion; (l) a diamine or diammonium salt
having the formula: 45wherein R.sup.1, R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 are independently hydrogen or hydrocarbyl or
substituted hydrocarbyl having from 1 to about 30 carbon atoms,
R.sup.2 in each of the m (R.sup.2O) and n (R.sup.2O) groups and
R.sup.9 are independently C.sub.2-C.sub.4 alkylene, R.sup.3 is
hydrocarbylene or substituted hydrocarbylene having from about 2 to
about 6 carbon atoms or --(R.sup.2O).sub.pR.sub.9--, m and n are
individually an average number from 0 to about 50, and p is an
average number from 0 to about 60; (m) an alkoxylated alcohol
having the formula:R.sup.1O--(R.sup.2O).sub.xR.sup.3 (18)wherein
R.sup.1 is hydrocarbyl or substituted hydrocarbyl having from 1 to
about 30 carbon atoms, R.sup.2 in each of the x (R.sup.2O) groups
is independently C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or
a linear or branched alkyl group having from 1 to about 4 carbon
atoms, and x is an average number from 1 to about 60; (n)
alkoxylated dialkylphenols having the formula: 46wherein R.sup.1
and R.sup.4 are independently hydrogen, or a linear or branched
alkyl group having from 1 to about 30 carbon atoms and at least one
of R.sup.1 and R.sup.4 is an alkyl group, R.sup.2 in each of the x
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, or a linear or branched alkyl group having
from 1 to about 4 carbon atoms, and x is an average number from 1
to about 60; (o) an alkyl alkoxylated phosphate having the formula:
47wherein R.sup.1 and R.sup.3 are independently a linear or
branched alkyl, linear or branched alkenyl, linear or branched
alkynyl, aryl, or aralkyl group having from about 4 to about 30
carbon atoms; R.sup.2 in each of the m (R.sup.2O) and the n
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene; and m
and n are independently from 1 to about 30; (p) an alkyl
alkoxylated phosphate having the formula: 48wherein R.sup.1 is a
linear or branched alkyl, linear or branched alkenyl, linear or
branched alkynyl, aryl, or aralkyl group having from about 8 to
about 30 carbon atoms; R.sup.2 in each of the m (R.sup.2O) groups
is independently C.sub.2-C.sub.4 alkylene; and m is from 1 to about
30; and mixtures or combinations thereof.
54. A herbicidal particulate solid concentrate which may be
dissolved or dispersed in water to provide an aqueous herbicidal
application mixture for application to the foliage of a plant, the
concentrate comprising: glyphosate or a herbicidal derivative
thereof; and, pyridine analog or a herbicidal derivative thereof,
wherein the glyphosate (acid equivalent basis) and the pyridine
analog (acid equivalent basis) are present in a weight ratio of at
least 1:1, glyphosate being in excess.
55. The herbicidal particulate solid concentrate of claim 54
further comprising at least one surfactant.
56. The herbicidal particulate solid concentrate of claim 55
wherein said surfactant is selected from the group consisting of:
(a) a secondary or tertiary amine having the formula: 49wherein
R.sup.1 and R.sup.2 are hydrocarbyl having from 1 to about 30
carbon atoms, and R.sup.3 is hydrogen or hydrocarbyl having from 1
to about 30 carbon atoms; (b) a monoalkoxylated amine having the
formula: 50wherein R.sup.1 and R.sup.4 are independently
hydrocarbyl or substituted hydrocarbyl groups having from 1 to
about 30 carbon atoms or --R.sup.5SR.sup.6, R.sup.2 in each of the
x (R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, or a linear or branched alkyl group having
from 1 to about 4 carbon atoms, R.sup.5 is a linear or branched
alkyl group having from about 6 to about 30 carbon atoms, R.sup.6
is a hydrocarbyl or substituted hydrocarbyl group having from 4 to
about 15 carbon atoms and x is an average number from 1 to about
60; (c) a dialkoxylated quaternary ammonium salt having the
formula: 51wherein R.sup.1 is hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, R.sup.2 in each
of the x (R.sup.2O) and y (R.sup.2O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a linear or
branched alkyl group having from 1 to about 4 carbon atoms, R.sup.4
is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1
to about 30 carbon atoms, x and y are independently an average
number from 1 to about 40, and X- is an agriculturally acceptable
anion; (d) a monoalkoxylated quaternary ammonium salt having the
formula: 52wherein R.sup.1 and R.sup.5 are independently hydrogen
or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, R.sup.4 is hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, R.sup.2 in each of the x
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, or a linear or branched alkyl group having
from 1 to about 30 carbon atoms, x is an average number from 1 to
about 60, and X- is an agriculturally acceptable anion; (e) a
quaternary ammonium salt having the formula: 53wherein R.sup.1,
R.sup.3 and R.sup.4 are independently hydrogen or hydrocarbyl or
substituted hydrocarbyl having from 1 to about 30 carbon atoms,
R.sup.2 is hydrocarbyl or substituted hydrocarbyl having from 1 to
about 30 carbon atoms, and X- is an agriculturally acceptable
anion; (f) an ether amine having the formula: 54wherein R.sup.1 is
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms; R.sup.2 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 30 carbon atoms; R.sup.3 and
R.sup.4 are independently hydrogen, hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, or
--(R.sup.5O).sub.xR.sup.6, R.sup.5 in each of the x(R.sup.5--O)
groups is independently C.sub.2-C.sub.4 alkylene, R.sup.6 is
hydrogen, or a linear or branched alkyl group having from 1 to
about 4 carbon atoms, and x is an average number from 1 to about
50; (g) a diamine having the formula: 55wherein R.sup.1, R.sup.3,
R.sup.4 and R.sup.5 are independently hydrogen, hydrocarbyl or
substituted hydrocarbyl having from 1 to about 30 carbon atoms, or
--(R.sup.6O).sub.xR.sup.7; R.sup.2 and R.sup.8 are independently
hydrocarbylene or substituted hydrocarbylene having from 2 to about
30 carbon atoms, R.sup.6 in each of the x (R.sup.6O) and y
(R.sup.6O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.7 is hydrogen, or a linear or branched alkyl group having
from 1 to about 30 carbon atoms, x is an average number from 1 to
about 30, X is --O--, --N(R.sup.6)--, --C(O)--, --C(O)O--,
--OC(O)--, --N(R.sup.9)C(O)--, --C(O)N(R.sup.9)--, --S--, --SO--,
or --SO.sub.2--, y is 0 or an average number from 1 to about 30, n
and z are independently 0 or 1, and R.sup.9 is hydrogen or
hydrocarbyl or substituted hydrocarbyl; (h) an amine oxide having
the formula: 56wherein R.sup.1, R.sup.2 and R.sup.3 are
independently hydrogen, hydrocarbyl or substituted hydrocarbyl,
--(R.sup.4O).sub.xR.sup.5, or --R.sup.6(OR.sup.4).sub.xOR.sup.5;
R.sup.4 in each of the x (R.sup.4O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.5 is hydrogen, or a linear or
branched alkyl group having from 1 to about 30 carbon atoms,
R.sup.6 is hydrocarbylene or substituted hydrocarbylene having from
2 to about 6 carbon atoms, x is an average number from 1 to about
50, and the total number of carbon atoms in R.sup.1, R.sup.2 and
R.sup.3 is at least 8; (i) a dialkoxylated amine having the
formula: 57wherein R.sup.1 is a hydrocarbyl or substituted
hydrocarbyl having from about 6 to about 30 carbon atoms, or
--R.sup.4SR.sup.5, R.sup.4 and R.sup.2 in each of the x (R.sup.2O)
and the y (R.sup.2O) groups is independently C.sub.2-C.sub.4
alkylene, R.sup.3 is hydrogen, or a linear or branched alkyl group
having from 1 to about 4 carbon atoms, R.sup.5 is a linear or
branched alkyl group having from about 4 to about 15 carbon atoms,
and x and y are independently an average number from 1 to about 40;
(j) an aminated alkoxylated alcohol having the following chemical
structure: 58wherein R.sup.1, R.sup.7, R.sup.8, and R.sup.9 are
each independently hydrogen, hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, or
--(R.sup.11).sub.s(R.sup.3O).sub.vR.sup.10; X is --O--, --OC(O)--,
--C(O)O--, --N(R.sup.12)C(O)--, --C(O)N(R.sup.12)--, --S--, --SO--,
--SO.sub.2-- or --N(R.sup.9)--; R.sup.3 in each of the n (R.sup.3O)
groups and the v (R.sup.3O) groups is independently C.sub.2-C.sub.4
alkylene; R.sup.10 is hydrogen, or a linear or branched alkyl group
having from 1 to about 30 carbon atoms; n is an average number from
1 to about 60; v is an average number from 1 to about 50; R.sup.2
and R.sup.11 are each independently hydrocarbylene or substituted
hydrocarbylene having from 1 to about 6 carbon atoms; R.sup.4 is
hydrocarbylene or substituted hydrocarbylene having from 2 to about
6 carbon atoms; R.sup.12 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; m and s are
each independently 0 or 1; R.sup.6 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 30 carbon atoms,
--C(.dbd.NR.sup.12)--, --C(S)--, or --C(O)--; q is an integer from
0 to 5; and R.sup.5 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; (k) a
quaternary ammonium, sulfonium and sulfoxonium salt having the
formula: 59wherein R.sup.1, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and
R.sup.11 are independently hydrogen, hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, or
--(R.sup.13).sub.s(R.sup.3O).sub.vR.s- up.12; X is --O--,
--OC(O)--, --N(R.sup.14)C(O)--, --C(O)N(R.sup.14)--, --C(O)O--, or
--S--; R.sup.3 in each of the n (R.sup.3O) groups and v (R.sup.3O)
groups is independently C.sub.2-C.sub.4 alkylene; R.sup.12 is
hydrogen, or a linear or branched alkyl group having from 1 to
about 30 carbon atoms; n is an average number from 1 to about 60; v
is an average number from 1 to about 50; R.sup.2 and R.sup.13 are
each independently hydrocarbylene or substituted hydrocarbylene
having from 1 to about 6 carbon atoms; m and s are each
independently 0 or 1; R.sup.4 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 6 carbon atoms; R.sup.6 is
hydrocarbylene or substituted hydrocarbylene having from 2 to about
30 carbon atoms, --C(.dbd.NR.sup.12)--, --C(S)--, or --C(O)--;
R.sup.14 is hydrogen or hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, q is an integer from 0 to
5; R.sup.5 is hydrogen or hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms; and each A.sup.- is an
agriculturally acceptable anion; (l) a diamine or diammonium salt
having the formula: 60wherein R.sup.1, R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 are independently hydrogen or hydrocarbyl or
substituted hydrocarbyl having from 1 to about 30 carbon atoms,
R.sup.2 in each of the m (R.sup.2O) and n (R.sup.2O) groups and
R.sup.9 are independently C.sub.2-C.sub.4 alkylene, R.sup.3 is
hydrocarbylene or substituted hydrocarbylene having from about 2 to
about 6 carbon atoms or --(R.sup.2O).sub.pR.sub.9--, m and n are
individually an average number from 0 to about 50, and p is an
average number from 0 to about 60; (m) an alkoxylated alcohol
having the formula:R.sup.1O--(R.sup.2O).sub.xR.sup.3 (18)wherein
R.sup.1 is hydrocarbyl or substituted hydrocarbyl having from 1 to
about 30 carbon atoms, R.sup.2 in each of the x (R.sup.2O) groups
is independently C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or
a linear or branched alkyl group having from 1 to about 4 carbon
atoms, and x is an average number from 1 to about 60; (n) an
alkoxylated dialkylphenol having the formula: 61wherein R.sup.1 and
R.sup.4 are independently hydrogen, or a linear or branched alkyl
group having from 1 to about 30 carbon atoms and at least one of
R.sup.1 and R.sup.4 is an alkyl group, R.sup.2 in each of the x
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, or a linear or branched alkyl group having
from 1 to about 4 carbon atoms, and x is an average number from 1
to about 60; (o) an alkyl alkoxylated phosphate having the formula:
62wherein R.sup.1 and R.sup.3 are independently a linear or
branched alkyl, linear or branched alkenyl, linear or branched
alkynyl, aryl, or aralkyl group having from about 4 to about 30
carbon atoms; R.sup.2 in each of the m (R.sup.2O) and the n
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene; and m
and n are independently from 1 to about 30; (p) an alkyl
alkoxylated phosphate having the formula: 63wherein R.sup.1 is a
linear or branched alkyl, linear or branched alkenyl, linear or
branched alkynyl, aryl, or aralkyl group having from about 8 to
about 30 carbon atoms; R.sup.2 in each of the m (R.sup.2O) groups
is independently C.sub.2-C.sub.4 alkylene; and m is from 1 to about
30; and mixtures or combinations thereof.
57. The herbicidal particulate solid of claim 54 wherein the weight
ratio (a.e. basis) of glyphosate to pyridine analog is at least
about 8:1.
58. The herbicidal particulate solid of claim 54 wherein the weight
ratio (a.e. basis) of glyphosate to pyridine analog ranges from
about 8:1 to about 20:1.
59. A method for killing or controlling the growth of unwanted
plants comprising contacting the foliage of said plants with a
herbicidally effective amount of the herbicidal composition of any
one of claims 28, 33, 37, 38, 39, 42 or 46.
60. A method of killing or controlling weeds or unwanted vegetation
comprising: diluting the liquid concentrate of any one of claims 1,
6, 11, 16, 21, 22, 27 or 52 in a convenient amount of water to form
an application mixture; and applying a herbicidally effective
amount of the application mixture to the foliage of the weeds or
unwanted vegetation.
61. A method of killing or controlling weeds or unwanted vegetation
comprising: dissolving a solid particulate concentrate of claim 54
or 55 in a convenient amount of water to form an application
mixture; and applying a herbicidally effective amount of the
application mixture to the foliage of the weeds or unwanted
vegetation.
62. A method of killing or controlling weeds or unwanted plants
comprising: diluting an aqueous herbicidal concentrate composition
in an amount of water to form an application mixture; and applying
a herbicidally effective amount of the application mixture to
foliage of the weeds or unwanted plants, wherein the weeds or
unwanted plants comprise poison ivy, poison oak, kudzu, multiflora
rose, golden rod, blue fescue, red maple, and/or red oak, and the
aqueous herbicidal concentrate composition comprises glyphosate or
a herbicidal derivative thereof; a pyridine analog selected from
the group consisting of triclopyr, clopyralid, dithiopyr, thiazopyr
and picloram, or a herbicidal derivative thereof; and, at least one
surfactant.
Description
REFERENCE TO RELATED APPLICATION
[0001] This application claims priority from U.S. Provisional
Application Ser. No. 60/496,031 (filed on Apr. 22, 2003), and U.S.
Provisional Patent Application Ser. No. 60/552,065 (filed Mar. 10,
2004), the entire contents of which are incorporated herein by
reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates generally to herbicidal
compositions or formulations, and to methods of using such
compositions to kill, or control the growth and proliferation of,
unwanted plants. In particular, the present invention relates to
herbicidal compositions, as well as their methods of use, which
comprise N-phosphonomethylglycine, or a herbicidal derivative
thereof, and a pyridine analog, or a herbicidal derivative thereof,
optionally with one or more suitable surfactants. Such compositions
cause early visual symptoms of treatment and/or enhanced
effectiveness or control when applied to the foliage of plants.
[0003] Herbicidal compositions comprising the herbicide
N-phosphonomethyl-glycine or derivatives thereof ("glyphosate"),
are useful for suppressing the growth of, or killing, unwanted
plants such as grasses, weeds and the like. Glyphosate typically is
applied to the foliage of the target plant. After application the
glyphosate is absorbed by the foliar tissue of the plant and
translocated throughout the plant. Glyphosate noncompetitively
blocks an important biochemical pathway which is common to
virtually all plants, but which is absent in animals. Although
glyphosate is very effective in killing or controlling the growth
of unwanted plants, the uptake (i.e., absorption) of glyphosate by
the plant foliar tissue and translocation of glyphosate throughout
the plant is relatively slow. Visual symptoms that a plant has been
treated with glyphosate may not appear until one week or more after
treatment.
[0004] Compositions comprising glyphosate may be formulated with
one or more surfactants to enhance their effectiveness for foliar
application. When water is added to a composition formulated with
surfactants, the resulting sprayable composition more easily and
effectively covers the foliage (e.g., the leaves or other
photosynthesizing organs) of plants. Glyphosate salts, for example,
have been formulated with surfactants such as polyoxyalkylene-type
surfactants including, among other surfactants, polyoxyalkylene
alkylamines. Commercial formulations of glyphosate herbicide
marketed under the trademark ROUNDUP.RTM. have been formulated by
Monsanto with such a polyoxyalkylene alkylamine, in particular a
polyoxyethylene tallowamine.
[0005] As a result of the somewhat slow development of visual
symptoms that may result when glyphosate is utilized alone,
formulations or compositions containing glyphosate and another
herbicide have been suggested, in an attempt to achieve both early
visual symptoms of plant treatment and prolonged control of the
plant. For example, some have suggested using a tank mix
composition containing glyphosate and a contact herbicide, such as
a pyridine analog like triclopyr (i.e.,
[(3,5,6-trichloro-2-pyridinyl)oxy]acetic acid) or a herbicidal
derivative thereof. However, to-date, such tank mixes have
generally (i) employed relatively low weight ratios of glyphosate
to, for example, triclopyr (wherein glyphosate and triclopyr are
present in equal amounts, glyphosate is in a slight excess, or
triclopyr is in excess), and/or (ii) not utilized a surfactant
therein.
[0006] For example, R. K. Howell et al. (Southern Weed Science
Society Proceedings, 195-197 (1998)) disclose the preparation of a
tank mixture containing a surfactant TL90, Roundup Pro.RTM. and
Garlon.TM. 4, the glyphosate (in Roundup Pro.RTM.) and triclopyr
(in Garlon.TM. 4) being present in an apparent weight ratio of
approximately 1.3:1, respectively.
[0007] G. M. Wright et al. (North Central Weed Control Conference
Proceedings, vol. 38, 139 (1983)) disclose the preparation of a
tank mixture of glyphosate and triclopyr in the apparent absence of
a surfactant, the glyphosate and triclopyr, respectively, being
present in an apparent weight ratio of approximately 1.5:1.
[0008] M. L. McCormack et al. (Northeastern Weed Society
Proceedings, vol. 36, 209-214 (1982)) disclose the preparation of a
tank mixture of glyphosate and triclopyr in the apparent absence of
a surfactant, the glyphosate and triclopyr, respectively, being
present in an apparent weight ratio of approximately 1.4:1.
[0009] J. Lawrie et al. (Weed Research, vol. 33, 25-34, (1993)
appear to disclose the preparation of a tank mixture of glyphosate,
triclopyr and a surfactant-containing mixture, wherein the
glyphosate and triclopyr, respectively, appear to be present in a
weight ratio of approximately 1.67:1.
[0010] W. Harahap et al. (Biotrop Special Publication, no. 24,
317-24 (1986)) disclose the preparation of tank mixtures of
glyphosate and triclopyr or picloram, in the apparent absence of a
surfactant. In the tank mixtures, glyphosate and triclopyr are,
respectively, present in an apparent weight ratio of approximately
9.5:1 or 11.5:1, while glyphosate and picloram are present in an
apparent weight ratio of approximately 7.7:1.
[0011] S. H. Kay et al. (Southern Weed Science Society Proceedings,
291 (1992)) disclose the preparation of a tank mixture of
glyphosate and triclopyr in the apparent absence of a surfactant,
the glyphosate and triclopyr, respectively, being present in a
weight ratio of approximately 1:1.
[0012] A Roundup Pro.RTM. Supplemental Label (for application in
California using a helicopter, EPA Reg. No. 524-475, Monsanto
Company (1996)), discloses the optional preparation of a tank
mixture of Roundup Pro.RTM. and Garlon.TM. 4 in varying weight
ratios of glyphosate and triclopyr, respectively, as well as
varying concentrations related thereto.
[0013] Tank mixtures require the user to purchase and store each
herbicide used in the mixture separately, until the actual
preparation of such mixtures in the field. The user must also
measure out varying amounts of each herbicide used in the mixture.
Therefore, a pre-packaged mixture (i.e., a concentrate) which
already contains the desired herbicides in a single container may
be desirable in some instances. However, concentrates may be
difficult to prepare, for example when one of the herbicides is not
soluble or miscible with the same desired solvent (e.g.,
water).
[0014] The solubility or miscibility problems sometimes encountered
with concentrates may be overcome by preparing a concentrated
emulsion formulation. A concentrated emulsion formulation consists
of two phases and is a dispersion of one immiscible liquid (i.e.,
the discontinuous phase) in a second liquid (i.e., the continuous
phase). If the continuous phase is water, the emulsion is an
oil-in-water type emulsion and the water-immiscible liquid or
solution may be referred to as the "oil" phase (regardless of its
composition). In a concentrated emulsion formulation, the active
ingredient may be dissolved in an organic solvent along with added
emulsifiers and/or dispersants. When the concentrate is added to
water, the active ingredient becomes dispersed throughout the
water. Such a concentrate, in the form of a microemulsion, was
prepared in U.K. Patent Application No. GB 2 267 825 A, using a
slight excess of the isopropylamine salt of glyphosate relative to
the butoxyethyl ester of triclopyr (weight ratio of glyphosate to
triclopyr approximately 1.6:1), and a high load or amount of
triclopyr and two ethoxylated cocoamine surfactants, Ethomeen.TM.
C-15 and C-25 (approximately 100 g/L triclopyr and approximately
285 g/L total surfactant).
SUMMARY OF THE INVENTION
[0015] Briefly, therefore, the present invention is directed to an
aqueous herbicidal liquid concentrate, which may be diluted with
water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant. The concentrate comprises
glyphosate, or a herbicidal derivative thereof, in a concentration
of at least about 50 grams acid equivalent per liter, a pyridine
analog selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, and at least one surfactant, wherein (i) the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 1.7:1, and (ii)
when the glyphosate is predominantly in the form of a salt, said
salt is selected from the group consisting of a sodium salt, an
ammonium salt, an alkylammonium salt, a C.sub.3-16 alkanolammonium
salt, a di-ammonium salt, an alkylamine salt, a C.sub.3-16
alkanolamine salt, an alkylsulfonium salt, a sulfoxonium salt, and
combinations thereof.
[0016] The present invention is further directed to an aqueous
herbicidal liquid concentrate, which may be diluted with water to
provide an aqueous herbicidal application mixture for application
to the foliage of a plant. The concentrate comprises glyphosate, or
a herbicidal derivative thereof, in a concentration of at least
about 50 grams acid equivalent per liter, a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, and at least one surfactant, wherein (i) the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio ranging from at least 1.7:1 to
less than about 32:1, and (ii) when the glyphosate is predominantly
in the form of a salt, said salt is selected from the group
consisting of a sodium salt, an ammonium salt, an alkylammonium
salt, a C.sub.3-16 alkanolammonium salt, a di-ammonium salt, an
alkylamine salt, a C.sub.3-16 alkanolamine salt, an alkylsulfonium
salt, a sulfoxonium salt, and combinations thereof.
[0017] The present invention is still further directed to an
aqueous herbicidal liquid concentrate, which may be diluted with
water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant. The concentrate comprises
glyphosate, or a herbicidal derivative thereof, a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, and at least one surfactant in a concentration ranging
from about 1 grams to 283 grams per liter, wherein (i) the
glyphosate (acid equivalent basis) and the pyridine analog (acid
equivalent basis) are present in a weight ratio of at least 1:1,
glyphosate being in excess, and (ii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-16 alkanolamine
salt, an alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
[0018] The present invention is still further directed to an
aqueous herbicidal liquid concentrate, which may be diluted with
water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant. The concentrate comprises
glyphosate, or a herbicidal derivative thereof, a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, in a concentration ranging from about 1 gram to 99 grams
(acid equivalent basis) per liter, and at least one surfactant,
wherein (i) the glyphosate (acid equivalent basis) and the pyridine
analog (acid equivalent basis) are present in a weight ratio of at
least 1:1, glyphosate being in excess, and (ii) when the glyphosate
is predominantly in the form of a salt, said salt is selected from
the group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-16 alkanolamine
salt, an alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
[0019] The present invention is still further directed to an
aqueous herbicidal liquid concentrate, which may be diluted with
water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant. The concentrate comprises
glyphosate, or a herbicidal derivative thereof, a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, and at least one surfactant, wherein (i) the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 1:1, (ii) the
glyphosate (acid equivalent basis) and the surfactant are present
in a weight ratio of at least 1:1, wherein glyphosate is in excess
in both instances, and (iii) when the glyphosate is predominantly
in the form of a salt, said salt is selected from the group
consisting of a sodium salt, an ammonium salt, an alkylammonium
salt, a C.sub.3-16 alkanolammonium salt, a di-ammonium salt, an
alkylamine salt, a C.sub.3-16 alkanolamine salt, an alkylsulfonium
salt, a sulfoxonium salt, and combinations thereof.
[0020] The present invention is still further directed to an
aqueous herbicidal liquid concentrate, which may be diluted with
water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant. The concentrate comprises
glyphosate, or a herbicidal derivative thereof, and a pyridine
analog selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, wherein the glyphosate (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 1:1, glyphosate being in excess, and further
wherein (i) the pyridine analog or a herbicidal derivative thereof
is present at a concentration of not greater than 99 grams (acid
equivalent) per liter, and (ii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-16 alkanolamine
salt, an alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
[0021] The present invention is still further directed to an
aqueous herbicidal liquid concentrate, which may be diluted with
water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant. The concentrate comprises
glyphosate, or a herbicidal derivative thereof, and a pyridine
analog, or a herbicidal derivative thereof, wherein the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 1:1, glyphosate
being in excess, and further wherein (i) the glyphosate (acid
equivalent basis) or herbicidal derivative thereof is present at a
concentration of not greater than 165 grams (acid equivalent) per
liter, and (ii) when the glyphosate is predominantly in the form of
a salt, said salt is selected from the group consisting of a sodium
salt, an ammonium salt, an alkylammonium salt, a C.sub.3-16
alkanolammonium salt, a di-ammonium salt, an alkylamine salt, a
C.sub.3-16 alkanolamine salt, an alkylsulfonium salt, a sulfoxonium
salt, and combinations thereof.
[0022] The present invention is still further directed to an
aqueous herbicidal liquid concentrate which may be diluted with
water to provide an aqueous herbicidal application mixture for
application to the foliage of a plant. The concentrate comprises at
least one glyphosate salt predominantly in the form of potassium
glyphosate, monoethanolamine glyphosate, or a mixture thereof; a
pyridine analog selected from the group consisting of triclopyr,
clopyralid, fluroxypyr, dithiopyr, thiazopyr and picloram, or a
herbicidal derivative thereof; and, at least one surfactant in a
concentration less than 20 grams per liter; wherein the glyphosate
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 1:1, glyphosate
being in excess.
[0023] The present invention is further directed to an aqueous
herbicidal liquid concentrate, which may be diluted with water to
provide an aqueous herbicidal application mixture for application
to the foliage of a plant. The concentrate comprises glyphosate, or
a herbicidal derivative thereof, in a concentration of less than 65
grams acid equivalent per liter, picloram, or a herbicidal
derivative thereof, and at least one surfactant, wherein (i) the
glyphosate (acid equivalent basis) and the picloram (acid
equivalent basis) are present in a weight ratio of at least 1:1,
with glyphosate being in excess. Optionally, when the glyphosate is
predominantly in the form of a salt, said salt may be selected from
the group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-16 alkanolamine
salt, an alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
[0024] The present invention is still further directed to a method
of killing or controlling weeds or unwanted vegetation. The method
comprises diluting one of the preceding liquid concentrates in a
convenient amount of water to form an application mixture, and then
applying a herbicidally effective amount of the application mixture
to the foliage of the weeds or unwanted vegetation.
[0025] The present invention is still further directed to an
aqueous herbicidal composition useful for killing or controlling
the growth of unwanted plants. The composition comprises
glyphosate, or a herbicidal derivative thereof, a pyridine analog,
or a herbicidal derivative thereof, and at least one surfactant,
wherein (i) the glyphosate (acid equivalent basis) and the pyridine
analog (acid equivalent basis) are present in a weight ratio of at
least 7.6:1, and (ii) when the glyphosate is predominantly in the
form of a salt, said salt is selected from the group consisting of
a sodium salt, an ammonium salt, an alkylammonium salt, a
C.sub.3-16 alkanolammonium salt, a di-ammonium salt, an alkylamine
salt, a C.sub.3-16 alkanolamine salt, an alkylsulfonium salt, a
sulfoxonium salt, and combinations thereof.
[0026] The present invention is still further directed to an
aqueous herbicidal composition useful for killing or controlling
the growth of unwanted plants. The composition comprises
glyphosate, or a herbicidal derivative thereof, a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, in a concentration of not greater than 3.9 grams (acid
equivalent basis) per liter, and at least one surfactant, wherein
(i) the glyphosate (acid equivalent basis) and the pyridine analog
(acid equivalent basis) are present in a weight ratio of at least
about 1:1, glyphosate being in excess, and (ii) when the glyphosate
is predominantly in the form of a salt, said salt is selected from
the group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-16 alkanolamine
salt, an alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
[0027] The present invention is still further directed to an
aqueous herbicidal composition useful for killing or controlling
the growth of unwanted plants. The composition comprises
glyphosate, or a herbicidal derivative thereof, a pyridine analog
selected from the group consisting of triclopyr, clopyralid,
dithiopyr, thiazopyr and picloram, or a herbicidal derivative
thereof, and at least one surfactant, wherein (i) the surfactant
concentration is not greater than 3.9 grams per liter, (ii)
glyphosate (acid equivalent basis) and the pyridine analog (acid
equivalent basis) are present in a weight ratio of at least 3:1,
and (iii) when the glyphosate is predominantly in the form of a
salt, said salt is selected from the group consisting of a sodium
salt, an ammonium salt, an alkylammonium salt, a C.sub.3-16
alkanolammonium salt, a di-ammonium salt, an alkylamine salt, a
C.sub.3-16 alkanolamine salt, an alkylsulfonium salt, a sulfoxonium
salt, and combinations thereof.
[0028] The present invention is still further directed to an
aqueous herbicidal composition useful for killing or controlling
the growth of unwanted plants. The composition comprises
glyphosate, or a herbicidal derivative thereof, a pyridine analog,
or a herbicidal derivative thereof, and at least one surfactant,
wherein (i) the surfactant concentration is not greater than 6.6
grams per liter, (ii) glyphosate (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 5:1, and (iii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-16 alkanolamine
salt, an alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
[0029] The present invention is still further directed to an
aqueous herbicidal composition useful for killing or controlling
the growth of unwanted plants. The composition comprises
glyphosate, or a herbicidal derivative thereof, a pyridine analog,
or a herbicidal derivative thereof, and at least one surfactant,
wherein (i) the surfactant concentration is not greater than 9.3
grams per liter, (ii) glyphosate (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 7:1, and (iii) when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-16 alkanolamine
salt, an alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
[0030] The present invention is still further directed to an
aqueous herbicidal composition useful for killing or controlling
the growth of unwanted plants. The composition comprises glyphosate
or a herbicidal derivative thereof, a pyridine analog or a
herbicidal derivative thereof, and at least one surfactant, wherein
either (i) the glyphosate concentration (acid equivalent basis) is
not greater than 16.2 grams per liter, and glyphosate (acid
equivalent basis) and the pyridine analog (acid equivalent basis)
are present in a weight ratio of at least 4:1, or (ii) the
glyphosate concentration (acid equivalent basis) is not greater
than 23.8 grams per liter, and glyphosate (acid equivalent basis)
and the pyridine analog (acid equivalent basis) are present in a
weight ratio of at least 6:1, and further when the glyphosate is
predominantly in the form of a salt, said salt is selected from the
group consisting of a sodium salt, an ammonium salt, an
alkylammonium salt, a C.sub.3-16 alkanolammonium salt, a
di-ammonium salt, an alkylamine salt, a C.sub.3-16 alkanolamine
salt, an alkylsulfonium salt, a sulfoxonium salt, and combinations
thereof.
[0031] The present invention is still further directed to an
aqueous herbicidal composition useful for killing or controlling
the growth of unwanted plants. The concentrate comprises at least
one glyphosate salt predominantly in the form of potassium
glyphosate, monoethanolamine glyphosate, or a mixture thereof; and
a pyridine analog selected from the group consisting of triclopyr,
clopyralid, fluroxypyr, dithiopyr, thiazopyr and picloram, or a
herbicidal derivative thereof; wherein (i) the glyphosate salt is
present in a concentration less than 180 grams acid equivalent per
liter and the glyphosate salt (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 1:1, glyphosate being in excess; (ii) the
glyphosate salt is present in a concentration less than 240 grams
acid equivalent per liter and the glyphosate salt (acid equivalent
basis) and the pyridine analog (acid equivalent basis) are present
in a weight ratio of at least 2:1; (iii) the glyphosate salt is
present in a concentration less than 270 grams acid equivalent per
liter and the glyphosate salt (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 3:1; (iv) the glyphosate salt is present in a
concentration less than 288 grams acid equivalent per liter and the
glyphosate salt (acid equivalent basis) and the pyridine analog
(acid equivalent basis) are present in a weight ratio of at least
4:1; (v) the glyphosate salt is present in a concentration less
than 300 grams acid equivalent per liter and the glyphosate salt
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 5:1; (vi) the
glyphosate salt is present in a concentration less than 308 grams
acid equivalent per liter and the glyphosate salt (acid equivalent
basis) and the pyridine analog (acid equivalent basis) are present
in a weight ratio of at least 6:1; (vii) the glyphosate salt is
present in a concentration less than 315 grams acid equivalent per
liter and the glyphosate salt (acid equivalent basis) and the
pyridine analog (acid equivalent basis) are present in a weight
ratio of at least 7:1; (viii) the glyphosate salt is present in a
concentration less than 320 grams acid equivalent per liter and the
glyphosate salt (acid equivalent basis) and the pyridine analog
(acid equivalent basis) are present in a weight ratio of at least
8:1; (ix) the glyphosate salt is present in a concentration less
than 324 grams acid equivalent per liter and the glyphosate salt
(acid equivalent basis) and the pyridine analog (acid equivalent
basis) are present in a weight ratio of at least 9:1; or (x) the
glyphosate salt is present in a concentration less than 326 grams
acid equivalent per liter and the glyphosate salt (acid equivalent
basis) and the pyridine analog (acid equivalent basis) are present
in a weight ratio of at least 10:1.
[0032] The present invention is still further directed to a method
for killing or controlling the growth of unwanted plants. The
method comprises contacting the foliage of said plants with a
herbicidally effective amount of one of the previously described
aqueous herbicidal compositions.
[0033] The present invention is still further directed to a
herbicidal particulate solid concentrate which may be dissolved or
dispersed in water to provide an aqueous herbicidal application
mixture for application to the foliage of a plant. The solid
concentrate comprises glyphosate, or a herbicidal derivative
thereof, and a pyridine analog, or a herbicidal derivative thereof,
wherein a weight ratio (a.e. basis) of glyphosate to the pyridine
analog is at least about 1:1, glyphosate being in excess, and
further wherein when the glyphosate is predominantly in the form of
a salt. Optionally, one or more surfactants may be present in the
herbicidal particulate solid concentrate.
[0034] The present invention is still further directed to a method
of killing or controlling weeds or unwanted vegetation. The method
comprises diluting or dissolving the previously described solid
particulate concentrate in a convenient amount of water to form an
application mixture, and then applying a herbicidally effective
amount of the application mixture to the foliage of the weeds or
unwanted vegetation.
[0035] The present invention is still further directed to one or
more of the previously noted methods for killing or controlling the
growth of unwanted plants which comprises contacting the foliage of
said plants with such an aqueous herbicidal composition, wherein
said herbicidal composition is brought into contact with, or
applied to, said foliage using means other than a helicopter.
[0036] The present invention is still further directed to a method
of killing or controlling weeds or unwanted plants. The method
comprises diluting an aqueous herbicidal concentrate composition in
an amount of water to form an application mixture; and, applying a
herbicidally effective amount of the application mixture to foliage
of the weeds or unwanted plants, wherein the weeds or unwanted
plants comprise poison ivy, poison oak, kudzu, multiflora rose,
golden rod, blue fescue, red maple, and/or red oak, and the aqueous
herbicidal concentrate composition comprises glyphosate or a
herbicidal derivative thereof; a pyridine analog selected from the
group consisting of triclopyr, clopyralid, dithiopyr, thiazopyr and
picloram, or a herbicidal derivative thereof; and, at least one
surfactant.
[0037] The present invention is still further directed to one or
more of the previously described aqueous herbicidal liquid
concentrates, aqueous herbicidal compositions, herbicidal
particulate solid concentrates, and methods for the use thereof,
wherein said pyridine analog is triclopyr, a derivative thereof, or
some combination which includes triclopyr.
[0038] The present invention is still further directed to one or
more of the previously described aqueous herbicidal liquid
concentrates, aqueous herbicidal compositions, herbicidal
particulate solid concentrates, and methods for the use thereof,
wherein said pyridine analog is clopyralid, a derivative thereof,
or some combination which includes clopyralid.
[0039] The present invention is still further directed to one or
more of the previously described aqueous herbicidal liquid
concentrates, aqueous herbicidal compositions, herbicidal
particulate solid concentrates, and methods for the use thereof,
wherein said pyridine analog is dithiopyr, a derivative thereof, or
some combination which includes dithiopyr.
[0040] The present invention is still further directed to one or
more of the previously described aqueous herbicidal liquid
concentrates, aqueous herbicidal compositions, herbicidal
particulate solid concentrates, and methods for the use thereof,
wherein said pyridine analog is thiazopyr, a derivative thereof, or
some combination which includes thiazopyr.
[0041] The present invention is still further directed, where
appropriate, to one or more of the previously described aqueous
herbicidal liquid concentrates, aqueous herbicidal compositions,
herbicidal particulate solid concentrates, and methods for the use
thereof, wherein said pyridine analog is picloram, a derivative
thereof, or some combination which includes picloram.
[0042] The present invention is still further directed, where
appropriate, to one or more of the previously described aqueous
herbicidal liquid concentrates, aqueous herbicidal compositions,
herbicidal particulate solid concentrates, and methods for the use
thereof, wherein said pyridine analog is fluroxypyr, a derivative
thereof, or some combination which includes fluroxypyr.
[0043] The present invention is still further directed, where
appropriate, to one or more of the previously described aqueous
herbicidal liquid concentrates, aqueous herbicidal compositions,
herbicidal particulate solid concentrates, and methods for the use
thereof, wherein said pyridine analog is a combination or mixture
of one or more of triclopyr, fluroxypyr, dithiopyr, thiazopyr,
picloram, or derivatives thereof.
[0044] The present invention is still further directed, where
appropriate, to one or more of the previously described aqueous
herbicidal liquid concentrates, aqueous herbicidal compositions,
herbicidal particulate solid concentrates, and methods for the use
thereof, wherein said pyridine analog is a combination or mixture
of triclopyr and clopyralid, or derivatives thereof.
[0045] The present invention is still further directed, where
appropriate, to one or more of the previously described aqueous
herbicidal liquid concentrates, aqueous herbicidal compositions,
herbicidal particulate solid concentrates, and methods for the use
thereof, wherein said pyridine analog is a combination or mixture
of one or more of triclopyr, clopyralid, fluroxypyr, or derivatives
thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0046] According to the present invention, coherbicidal
compositions or formulations containing glyphosate or a derivative
thereof, a pyridine analog (e.g., triclopyr, clopyralid,
fluroxypyr, dithiopyr, thiazopyr, picloram, etc., or a combination
thereof) or a derivative thereof, and optionally a suitable
surfactant, are provided that are advantageous for a number of
reasons, including rapid uptake by the target plant, early visual
symptoms of plant treatment, and control of a broad spectrum of
plant species, as well as enhanced, more consistent control of
unwanted plants. Accordingly, in at least some embodiments, lower
application rates may potentially be used for the pyridine analog
and/or the surfactant(s) applied, without a loss of effectiveness
of plant control.
[0047] I. Glyphosate and Pyridine Analog Coherbicides
[0048] A. Coherbicide Combinations and Forms
[0049] The compositions or formulations of the present invention
comprise at least two herbicides, and optionally at least one
surfactant. A first component of the compositions of the present
invention may be, for example, N-phosphonomethylglycine
("glyphosate"), a salt or adduct thereof, or a compound which is
converted to glyphosate in plant tissues or which otherwise
provides glyphosate ion. In this regard it is to be noted that the
term "glyphosate," when used herein, is to be understood to
encompass such derivatives unless the context requires
otherwise.
[0050] Glyphosate salts that can be used according to this
invention include but are not restricted to, for example, alkali
metal salts, for example sodium and potassium salts, ammonium
salts, alkylammonium salts (e.g., C.sub.1-16 alkylammonium, or
alternatively C.sub.3-16 alkylammonium), alkanolammonium salts
(e.g., C.sub.1-16 alkanolammonium, or alternatively C.sub.3-16
alkanolammonium), di-ammonium salts such as dimethylammonium,
alkylamine salts, for example dimethylamine and isopropylamine
salts, alkanolamine salts (e.g., C.sub.1-16 alkanolamine, or
alternatively C.sub.3-16 alkanolamine), for example ethanolamine
salts, alkylsulfonium salts (e.g., C.sub.1-16 alkylsulfonium, for
example trimethylsulfonium salts), sulfoxonium salts, and mixtures
or combinations thereof. For some preferred embodiments, preferred
glyphosate salts include for example the potassium salt,
isopropylamine salt, ammonium salt, di-ammonium salt, sodium salt,
monoethanolamine salt, and trimethylsulfonium salt, as well as
combinations thereof. For still other preferred embodiments,
glyphosate is predominantly in the form of a salt other than a
potassium salt or a monoethanolamine or monoethanolammonium salt;
that is, in an alternative preferred embodiment glyphosate is a
salt predominantly in the form of the isopropylamine salt, the
ammonium salt, the di-ammonium salt, the sodium salt, the
trimethylsulfonium salt, or some combination thereof.
[0051] The herbicidal properties of N-phosphonomethylglycine and
its derivatives were first discovered by Franz, then disclosed and
patented in U.S. Pat. No. 3,799,758, issued Mar. 26, 1974. A number
of herbicidal salts of N-phosphonomethylglycine were patented by
Franz in U.S. Pat. No. 4,405,531, issued Sep. 20, 1983. The
disclosures of both of these patents are hereby incorporated by
reference.
[0052] Various salts of N-phosphonomethylglycine are commercially
significant, in part because they are water soluble. Many of the
salts listed herein are highly water soluble, thereby allowing for
highly concentrated solutions that can be diluted at the site of
use. In accordance with the methods of this invention, as they
pertain to glyphosate herbicide, a solution containing a
herbicidally effective amount of glyphosate, and other components
as described elsewhere herein (e.g., a pyridine analog, and
optionally a surfactant), is applied to the foliage of plants.
[0053] A pyridine analog or derivative thereof (i.e., an acid, a
salt or an ester form thereof), such as one or more of those
disclosed in U.S. Pat. No. 4,692,184 (which is incorporated in its
entirety herein by reference for all relevant purposes), is another
component of the composition of the present invention. In this
regard it is to be noted that the phrase "pyridine analogs", as
well as variations thereof, is intended to generally refer to a
class of herbicides that includes, for example: triclopyr (i.e.,
[(3,5,6-trichloro-2-pyridinyl)oxy]acetic acid), clopyralid (i.e.,
3,6-dichloro-2-pyridine carboxylic acid), fluroxypyr (i.e.,
[(4-amino-3,5-dichoro-6-fluoro-pyridyl)oxy]aetic acid), dithiopyr
(i.e.,
S,S-dimethylester-2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluo-
romethyl)-3,5-pyridine dicarbothioic acid), thiazopyr (i.e., methyl
2-(difluoromethyl)-5-(4,5-dihydro-2-thiazolyl)-4-(2-methyl propyl
)-6-(trifluoromethyl)-3-pyridine carboxylate), and picloram (i.e.,
4-amino-3,5,6-trichloropicolinic acid), as well as derivatives
thereof, in all of their various forms, including for example the
acid, the salt (e.g., amine salt, such as monoethanolamine or
triethylamine), and the ester (e.g., butoxyethyl ester). Such
compounds may be characterized, in one aspect of the present
invention, by the rapid symptomology and more consistent control
they impart.
[0054] In this regard it is to be noted that the present invention
encompasses essentially any formulation disclosed herein (e.g.,
concentrate, solid or tank mix) which comprises glyphosate and any
one of triclopyr, clopyralid, fluroxypyr, dithiopyr, thiazopyr,
picloram, or a derivative thereof, as well as any combination or
mixture which includes any one, two, there, four, five or six of
these pyridine analogs. Exemplary co-herbicidal combinations are
set forth in greater detail in Coherbicide Tables A-E, below (which
illustrate that glyphosate, or one of its salts, can be combined
with pyridine analog herbicides to form a herbicidal composition
comprising two to seven actives, wherein: G=glyphosate;
Tr=triclopyr; C=clopyralid; F=fluroxypyr; D=dithiopyr;
Th=thiazopyr; P=picloram; and "Active No." is a herbicide
combination reference number):
1TABLE A Glyphosate in combination with one pyridine analog
herbicide Active No. Herbicides 1 G + Tr 2 G + C 3 G + F 4 G + D 5
G + Th 6 G + P
[0055]
2TABLE B Glyphosate in combination with two pyridine analog
herbicides Active No. Herbicides 7 G + Tr + P 8 G + Tr + C 9 G + Tr
+ D 10 G + Tr + Th 11 G + Tr + F 12 G + P + C 13 G + P + D 14 G + P
+ Th 15 G + P + F 16 G + C + D 17 G + C + Th 18 G + C + F 19 G + D
+ Th 20 G + D + F 21 G + Th + F
[0056]
3TABLE C Glyphosate in combination with three pyridine analog
herbicides Active No. Herbicides 22 G + Tr + P + C 23 G + Tr + P +
D 24 G + Tr + P + Th 25 G + Tr + P + F 26 G + Tr + C + D 27 G + Tr
+ C + Th 28 G + Tr + C + F 29 G + Tr + D + Th 30 G + Tr + D + F 31
G + Tr + Th + F 32 G + P + C + D 33 G + P + C + Th 34 G + P + C + F
35 G + P + D + Th 36 G + P + D + F 37 G + P + Th + F 38 G + C + D +
Th 39 G + C + D + F 40 G + C + Th + F 41 G + D + Th + F
[0057]
4TABLE D Glyphosate in combination with four pyridine analog
herbicides Active No. Herbicides 42 G + Tr + P + C + D 43 G + Tr +
P + C + Th 44 G + Tr + P + C + F 45 G + Tr + P + D + Th 46 G + Tr +
P + D + F 47 G + Tr + P + Th + F 48 G + Tr + C + D + Th 49 G + Tr +
C + D + F 50 G + Tr + C + Th + F 51 G + Tr + D + Th + F 52 G + P +
C + D + Th 53 G + P + C + D + F 54 G + P + C + Th + F 55 G + P + D
+ Th + F 56 G + C + D + Th + F -- --
[0058]
5TABLE E Glyphosate in combination with five pyridine analog
herbicides Active No. Herbicides 57 G + Tr + P + C + D + Th 58 G +
Tr + P + C + D + F 59 G + Tr + P + C + Th + F 60 G + Tr + P + D +
Th + F 61 G + Tr + C + D + Th + F 62 G + P + C + D + Th + F
[0059] In one preferred embodiment, the pyridine analog is selected
from the group consisting of triclopyr, clopyralid, dithiopyr,
thiazopyr, picloram, or some combination thereof. In an alternative
preferred embodiment, the pyridine analog is selected from the
group consisting of triclopyr, clopyralid, dithiopyr, thiazopyr, or
some combination thereof. In yet another preferred embodiment, the
pyridine analog is selected from the group consisting of triclopyr,
clopyralid, dithiopyr, or some combination thereof. In yet another
preferred embodiment, the pyridine analog is selected from the
group consisting of triclopyr, clopyralid, or a combination
thereof. In yet another preferred embodiment, the pyridine analog
is selected from the group consisting of triclopyr, dithiopyr,
thiazopyr, or some combination thereof. In yet another preferred
embodiment, the pyridine analog is selected from the group
consisting of triclopyr, clopyralid, fluroxypyr, or some
combination thereof.
[0060] With respect to the ester and salt forms of the pyridine
analogs or derivatives thereof of the present invention, it is to
be noted that the present invention encompasses essentially any
such ester or salt known to one of ordinary skill in the art, or
which may be prepared thereby using techniques known in the art.
Exemplary salts may include alkali metal salts, for example sodium
and potassium salts, ammonium salts, alkylammonium salts (e.g.,
C.sub.1-16 alkylammonium), alkanolammonium salts (e.g., C.sub.1-16
alkanolammonium), di-ammonium salts such as dimethylammonium,
alkylamine salts, for example dimethylamine and isopropylamine
salts, alkanolamine salts, for example ethanolamine salts,
alkylsulfonium salts (e.g., C.sub.1-16 alkylsulfonium, for example
trimethylsulfonium salts), sulfoxonium salts, and mixtures or
combinations thereof.
[0061] B. Concentrations and Ratios
[0062] The relative amounts of glyphosate and the pyridine analog
(e.g., triclopyr, clopyralid, fluroxypyr, dithiopyr, thiazopyr,
picloram, etc., or a combination thereof) present in a contemplated
herbicidal composition (i.e., a particulate solid concentrate, or
liquid concentrate, or alternatively a ready-to-use, or tank-mix,
composition) may vary depending upon many factors, including for
example the plant species to be controlled and the method of
application. Generally speaking, however, the concentrations of
these herbicides, and optionally a surfactant and/or some other
additive (as described elsewhere herein), in the herbicidal
compositions of the invention is sufficient to provide at least
about 70% control (as determined by means known in the art) within
about 50 days, preferably about 40 days, more preferably about 30
days, still more preferably about 20 days, still more preferably
about 15 days, still more preferably about 10 days, still more
preferably about 5 days, and even still more preferably about 1
day, or less, after application of the composition to a plant. In a
more preferred embodiment, the concentration of these herbicides,
and optionally a surfactant and/or some other additive, in the
herbidical compositions of the invention is sufficient to provide
at least about 80%, more preferably at least about 85%, still more
preferably at least about 90%, and still more preferably at least
about 95%, control, or more, within about 50 days, preferably about
40 days, more preferably about 30 days, still more preferably about
20 days, still more preferably about 15 days, still more preferably
about 10 days, still more preferably about 5 days, and even still
more preferably about 1 day, or less, after application of the
composition to a plant.
[0063] Additionally, the concentrations of these herbicides, and
optionally a surfactant and/or some other additive (as described
elsewhere herein), in the herbicidal compositions of the invention
is sufficient to provide at least about 70% control of plant
regrowth (as determined by means known in the art) for at least
about 20, preferably at least about 30, more preferably at least
about 40, still more preferably at least about 50, still more
preferably at least about 60, still more preferably at least about
70, still more preferably at least about 80, or even still more
preferably at least about 90, days after application of the
composition to a plant. In a more preferred embodiment, the
concentrations of these herbicides, and optionally a surfactant
and/or some other additive, in the herbidical compositions of the
invention is sufficient to provide at least about 80%, more
preferably at least about 85%, still more preferably at least about
90%, or still more preferably at least about 95% control, or more,
for at least about 20, more preferably at least about 30, still
more preferably at least about 40, still more preferably at least
about 50, still more preferably at least about 60, still more
preferably at least about 70, still more preferably at least about
80, or even still more preferably at least about 90, days after
application to the plant.
[0064] Accordingly, in some embodiments of the present invention
(e.g., the concentrate herbicidal composition), the glyphosate
concentration may be at least about 50 grams, preferably at least
about 75 grams, more preferably at least about 100 grams, still
more preferably at least about 125 grams, still more preferably at
least about 150 grams, still more preferably at least about 175
grams, still more preferably at least about 200 grams, still more
preferably at least about 225 grams, still more preferably at least
about 250 grams, (acid equivalent) per liter, or more (e.g., at
least about 300 grams, at least about 350 grams, at least about 400
grams, at least about 450 grams, at least about 500 grams, at least
550 grams, at least 600 grams per liter, or more). The glyphosate
concentration may therefore range from, for example, about 50 to
about 500 grams (a.e.) per liter, from about 100 to about 400 grams
per liter, from about 150 to about 300 grams per liter, or from
about 175 to about 250 grams per liter.
[0065] In an alternative embodiment, the concentration of
glyphosate may be no greater than 165 grams per liter (e.g., no
greater than 160 grams per liter, 155 grams per liter, 150 grams
per liter, 140 grams per liter, or even no greater than about 130,
about 120, about 110, about 100, about 75 grams per liter or less).
The glyphosate concentration may therefore range, for example, from
about 100 to no greater than 160 grams per liter, or from about 110
to no greater than 150 grams per liter.
[0066] In still other embodiments (e.g., a ready-to-use
composition, also known and referred to herein as a tank mix
composition), the glyphosate concentration may be less than about
50, preferably less than about 45, more preferably less than about
40, still more preferably less than about 35, still more preferably
less than about 30, or even still more preferably less than about
25 grams (a.e.) per liter (e.g., about 2, about 4, about 6, about
8, about 10, about 12, about 14, about 16, about 18 or about 20
grams (a.e.) per liter). Accordingly, the glyphosate concentration
may range, for example, from about 2 to about 50 grams (a.e.) per
liter, from about 4 to about 25, from about 6 to about 15, or from
about 8 to about 12 grams (a.e.) per liter. In some instances, such
as wherein:
[0067] (i) the weight ratio (a.e. to a.e.) of glyphosate to the
pyridine analog is at least 4:1 (e.g., at least about 5:1, 6:1,
7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 20:1, 40:1,
60:1, 80:1, or even 100:1), the concentration of glyphosate may be
no greater than 16.2 grams (a.e.) per liter (e.g., no greater than
about 16, about 15.5, about 15, about 14.5, about 14, about 13.5,
about 13, about 12.5, about 12, about 11.5, about 11, about 10.5,
about 10, about 9.5, about 9, about 8.5, about 8, about 7.5, about
7, about 6.5, about 6, about 5.5, about 5, etc., the concentration
thus ranging from, for example, about 5 to about 16, from about 7
to about 14, or from about 8 to about 12, grams (a.e.) per liter);
exemplary combinations include a ratio of at least 4:1, about 8:1,
or even about 10:1 with a glyphosate concentration of less than
about 15 grams (a.e.) per liter, 12 grams (a.e.) per liter, 10
grams (a.e.) per liter, or even 8 grams (a.e.) per liter;
and/or
[0068] (ii) the weight ratio (a.e. to a.e.) of glyphosate to
pyridine analog is at least 6:1 (e.g., at least about 7:1, 8:1,
9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 20:1, 40:1, 60:1, 80:1, or
even 100:1), the concentration of glyphosate may be no greater than
23.8 grams (a.e.) per liter (e.g., no greater than about 23.5,
about 23, about 22.5, about 22, about 21.5, about 21, about 20.5,
about 20, about 19.5, about 19, about 18.5, about 18, about 17.5,
about 17, about 16.5, about 16, about 15.5, about 15, about 14.5,
about 14, about 13.5, about 13, about 12.5, about 12, about 11.5,
about 11, about 10.5, about 10, about 9.5, about 9, about 8.5,
about 8, about 7.5, about 7, about 6.5, about 6, about 5.5, about
5, etc., the concentration thus ranging from, for example, about 5
to about 22, from about 6 to about 20, or from about 8 to about 15,
grams (a.e.) per liter); exemplary combinations include a ratio of
at least 6:1, about 8:1, or even about 10:1 with a glyphosate
concentration of less than about 20 grams (a.e.) per liter, 15
grams (a.e.) per liter, 12 grams (a.e.) per liter, 10 grams (a.e.)
per liter, or even 8 grams (a.e.) per liter.
[0069] With respect to the glyphosate concentration, it is to be
noted that as the concentration of glyphosate increases, the
concentration of one or more other ingredients in the present
composition may be reduced to maintain the solubility of one or
more of the ingredients therein (i.e., to ensure these ingredients
remain in solution).
[0070] The concentration of the pyridine analog in the herbicidal
composition of the present invention may also vary. For example,
the concentration may preferably be sufficient to provide visual
symptoms of herbicide treatment within about 5 days, preferably
about 4 days, or more preferably about 3 days after application of
the composition to the plant, and in some instances may be
sufficient to provide such symptoms within about 2 days, about 1
day or even less, after the application. However, in this regard it
is to be noted that the concentration of the pyridine analog is
also preferably controlled, such that it is not substantially
antagonistic to the herbicidal activity of the glyphosate, or
glyphosate derivative, within the composition.
[0071] Accordingly, in some embodiments of the present invention
(e.g., the concentrate herbicidal composition), the concentration
of the pyridine analog may be, for example, at least about 1, about
2, about 4, about 6, about 8, about 10, about 15, about 20, about
25, about 30, about 35, about 40, about 45, about 50, about 60,
about 70, about 80, about 90, about 100 or more grams (a.e.) per
liter. The concentration of the pyridine analog may therefore
range, for example, from about 1 to about 99 or 100 grams (a.e.)
per liter (e.g., about 1 to about 99 or 100, about 2 to about 80,
about 4 to about 60, about 6 to about 40, or about 8 to about 20,
grams (a.e.) per liter).
[0072] In these or other embodiments of the present invention, it
is to be noted that the concentration may alternatively be not
greater than 99 grams (a.e.) per liter (e.g., not greater than
about 95, about 90, about 85, about 80, about 75, about 70, about
65, about 60, about 55, about 50, about 40, about 30, about 20,
about 10, about 5 or less grams (a.e.) per liter). Accordingly, the
concentration of the pyridine analog may range from, for example,
about 1 to less than 99 grams (a.e.) per liter (e.g., from about 2
to less than about 80, from about 4 to less than about 60, from
about 6 to less than about 40, or from about 8 to less than about
20, grams (a.e.) per liter).
[0073] In still other embodiments (e.g., a ready-to-use
composition), the concentration of the pyridine analog may be less
than about 25, about 15 or even about 10 grams (a.e.) liter, the
concentration ranging for example from about 0.2 to about 10 grams
(a.e.) per liter, from about 0.4 to about 6, from about 0.6 to
about 4, or from about 0.8 to about 2 grams (a.e.) per liter.
Additionally, or alternatively, the concentration of the pyridine
analog may be not greater than 3.9 grams (a.e.) per liter (e.g.,
not greater than about 3.8, about 3.7, about 3.6, about 3.5, about
3.4, about 3.3, about 3.2, about 3.1, about 3, about 2.8, about
2.6, about 2.4, about 2.2, about 2, about 1.8, about 1.6, about
1.4, about 1.2, about 1, about 0.8, about 0.6, about 0.4, about 0.2
grams (a.e.) per liter or less, the concentration ranging for
example from about 0.2 to about 3.5 grams (a.e.) per liter, from
about 0.4 to about 3, from about 0.6 to about 2.5, or from about
0.8 to about 2 grams (a.e.) per liter).
[0074] With respect to the weight ratio (a.e. to a.e.) of
glyphosate to the pyridine analog, generally speaking this is
greater than about 1:1 (i.e., glyphosate is in excess); that is,
this ratio may be at least about 1.1:1, about 1.2:1, about 1.3:1,
about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1,
about 1.9:1, about 2:1, about 2.2:1, about 2.4:1, about 2.6:1,
about 2.8:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1,
about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about
13:1, about 14:1, about 15:1, about 20:1, about 25:1, about 30:1,
about 35:1, about 40:1, about 45:1, about 50:1 or more (e.g., about
60:1, about 70:1, about 80:1, about 90:1 or even about 100:1).
Accordingly, this ratio may range from about 1:1 to about 100:1,
from about 2:1 to about 80:1, from about 4:1 to about 60:1, from
about 6:1 to about 40:1, or from about 8:1 to about 20:1.
[0075] Alternatively, in some embodiments (e.g., a ready-to-use
composition), this ratio may be at least 7.6:1, and preferably may
be at least about 7.7:1, about 7.8:1, about 7.9:1, about 8:1, about
8.2:1, about 8.4:1, about 8.6:1, about 8.8:1, about 9:1, about
9.2:1, about 9.4:1, about 9.6:1, about 9.8:1, about 10:1 or more
(e.g., about 11:1, about 12:1, about 13:1, about 14:1, about 15:1,
about 20:1, about 25:1, about 30:1, about 35:1, about 40:1, about
45:1, about 50:1, about 60:1, about 70:1, about 80:1, about 90:1 or
even about 100:1). Accordingly, this ratio ranges from, for
example, about 7.8:1 to about 20:1, from about 8:1 to about 15:1,
from about 8.4:1 to about 14:1, or about 9:1 to about 12:1.
[0076] Additionally, in yet other alternative embodiments (e.g.,
concentrate or ready-to-use compositions), wherein for example
picloram is used, the ratio of glyphosate to pyridine analog (e.g.,
picloram) may be greater than about 1:1 and less than about 32:1,
range for example from about 5:1 to about 30:1, from about 10:1 to
about 25:1, from about 11:1 to about 20:1, from about 12:1 to about
18:1, or from about 14:1 to about 16:1.
[0077] In view of the foregoing, and as further described elsewhere
herein, it is to be noted that the concentration of glyphosate, the
concentration of the pyridine analog (e.g., triclopyr, clopyralid,
fluroxypyr, dithiopyr, thiazopyr, picloram, etc., or a combination
thereof), the weight ratio of glyphosate to the pyridine analog,
and/or the various ranges associated therewith, may be other than
herein described without departing from the scope of the present
invention.
[0078] It is to be further noted that the various concentrations of
the pyridine analog provided herein, as well as the various ratios
of glyphosate to the pyridine analog, are intended to apply
indepedently to each analog; that is, although not specifically
recited, it is to be noted that each concentration, concentration
range, ratio, etc. noted herein is intended to apply independently
triclopyr, clopyralid, fluroxypyr, dithiopyr, thiazopyr, picloram,
etc., or a combination thereof.
[0079] II. Surfactants
[0080] Various surfactants may be effective in formulating the
herbicidal compositions or concentrates of the present invention,
including for example the nonionic, cationic, anionic and
amphoteric surfactants as described below, as well as mixtures
thereof.
[0081] Cationic surfactants effective in such glyphosate
compositions or formulations include, for example:
[0082] (a) a secondary or tertiary amine having the formula: 1
[0083] wherein R.sup.1 and R.sup.2 are hydrocarbyl having from 1 to
about 30 carbon atoms, and R.sup.3 is hydrogen or hydrocarbyl
having from 1 to about 30 carbon atoms. In this context, preferred
R.sup.1, R.sup.2, and R.sup.3 hydrocarbyl groups are linear or
branched alkyl, linear or branched alkenyl, linear or branched
alkynyl, aryl, or aralkyl groups. Preferably, R.sup.1 is a linear
or branched alkyl or linear or branched alkenyl group having from
about 8 to about 30 carbon atoms, and R.sup.2 and R.sup.3 are
independently hydrogen or a linear or branched alkyl or linear or
branched alkenyl group having from 1 to about 6 carbon atoms. More
preferably, R.sup.1 is a linear or branched alkyl group having from
about 12 to about 22 carbon atoms, and R.sup.2 and R.sup.3 are
independently hydrogen, methyl, ethyl, or linear or branched
hydroxyalkyl groups having from 1 to about 6 carbon atoms.
[0084] In an alternative embodiment, the surfactant may have the
formula (1) wherein R.sup.1 is hydrocarbyl or substituted
hydrocarbyl having from about 8 to about 30 carbon atoms, R.sup.2
is a hydroxyalkyl, polyhydroxyalkyl or poly(hydroxyalkyl)alkyl
group, and R.sup.3 is hydrogen, hydroxyalkyl, polyhydroxyalkyl or
poly(hydroxyalkyl)alkyl. In this context, preferred R.sup.1
hydrocarbyl groups are linear or branched alkyl, linear or branched
alkenyl, linear or branched alkynyl, aryl, or aralkyl groups. In
one embodiment, R.sup.1 is a linear or branched alkyl, linear or
branched alkenyl, linear or branched alkynyl, aryl, or aralkyl
group having from about 8 to about 30 carbon atoms, R.sup.2 is a
linear or branched hydroxyalkyl group having from 1 to about 6
carbon atoms, and R.sup.3 is hydrogen or a linear or branched
hydroxyalkyl group having from 1 to about 6 carbon atoms.
Preferably, R.sup.1 is a linear or branched alkyl, linear or
branched alkenyl, linear or branched alkynyl, aryl, or aralkyl
group having from about 8 to about 22 carbon atoms, R.sup.2 is a
linear or branched hydroxyalkyl group having from 1 to about 4
carbon atoms, and R.sup.3 is hydrogen or a linear or branched
hydroxyalkyl group having from 1 to about 4 carbon atoms. More
preferably, R.sup.1 is a linear or branched alkyl, linear or
branched alkenyl, linear or branched alkynyl, aryl, or aralkyl
group having from about 8 to about 18 carbon atoms, R.sup.2 is
hydroxymethyl or hydroxyethyl, and R.sup.3 is hydrogen,
hydroxymethyl or hydroxyethyl.
[0085] (b) a monoalkoxylated amine having the formula: 2
[0086] wherein R.sup.1 and R.sup.4 are independently hydrocarbyl or
substituted hydrocarbyl groups having from 1 to about 30 carbon
atoms or --R.sup.5SR.sup.6, R.sup.2 in each of the x (R.sup.2O)
groups is independently C.sub.2-C.sub.4 alkylene, R.sup.3 is
hydrogen, or a linear or branched alkyl group having from 1 to
about 4 carbon atoms, R.sup.5 is a linear or branched alkyl group
having from about 6 to about 30 carbon atoms, R.sup.6 is a
hydrocarbyl or substituted hydrocarbyl group having from 4 to about
15 carbon atoms and x is an average number from 1 to about 60. In
this context, preferred R.sup.1, R.sup.4, and R.sup.6 hydrocarbyl
groups are linear or branched alkyl, linear or branched alkenyl,
linear or branched alkynyl, aryl, or aralkyl groups. In one
embodiment, R.sup.1 includes from about 7 to about 30 carbon atoms,
preferably from about 8 to about 22 carbon atoms, and the remaining
groups are as described above. Preferably, R.sup.1 and R.sup.4 are
independently a linear or branched alkyl or linear or branched
alkenyl group having from 1 to about 25 carbon atoms, R.sup.2 in
each of the x (R.sup.2O) groups is independently C.sub.2-C.sub.4
alkylene, R.sup.3 is hydrogen, methyl or ethyl, and x is an average
number from 1 to about 40. More preferably, R.sup.1 and R.sup.4 are
independently a linear or branched alkyl group having from 1 to
about 22 carbon atoms, R.sup.2 in each of the x (R.sup.2O) groups
is independently ethylene or propylene, R.sup.3is hydrogen or
methyl, and x is an average number from 1 to about 30. Even more
preferably, R.sup.1 is a linear or branched alkyl group having from
about 8 to about 22 carbon atoms and R.sup.4 is a linear or
branched alkyl group having from 1 to about 22 carbon atoms,
R.sup.2 in each of the x (R.sup.2O) groups is independently
ethylene or propylene, R.sup.3 is hydrogen or methyl, and x is an
average number from about 1 to about 10. Most preferably, R.sup.1
is a linear or branched alkyl group having from about 16 to about
22 carbon atoms and R.sup.4is methyl, R.sup.2 in each of the x
(R.sup.2O) groups is ethylene, R.sup.3 is hydrogen, and x is an
average number from about 1 to about 5, or R.sup.1 is a linear or
branched alkyl group having from about 8 to about 15 carbon atoms
and R.sup.4 is methyl, R.sup.2 in each of the x (R.sup.2O) groups
is ethylene, R.sup.3 is hydrogen, and x is an average number from
about 5 to about 10.
[0087] (c) a dialkoxylated quaternary ammonium salt having the
formula: 3
[0088] wherein R.sup.1 is hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, R.sup.2 in each of the x
(R.sup.2O) and y (R.sup.2O) groups is independently C.sub.2-C.sub.4
alkylene, R.sup.3 is hydrogen, or a linear or branched alkyl group
having from 1 to about 4 carbon atoms, R.sup.4 is hydrogen or
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, x and y are independently an average number from 1 to
about 40, and X- is an agriculturally acceptable anion. In this
context, preferred R.sup.1 and R.sup.4 hydrocarbyl groups are
linear or branched alkyl, linear or branched alkenyl, linear or
branched alkynyl, aryl, or aralkyl groups. Preferably, R.sup.1 and
R.sup.4 are independently a linear or branched alkyl or linear or
branched alkenyl group having from 1 to about 25 carbon atoms,
R.sup.2 in each of the x (R.sup.2O) and y (R.sup.2O) groups is
independently C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, methyl
or ethyl, and the sum of x and y is an average number from about 2
to about 30. More preferably, R.sup.1 and R.sup.4 are independently
a linear or branched alkyl group having from 1 to about 22 carbon
atoms, R.sup.2 in each of the x (R.sup.2O) and y (R.sup.2O) groups
is independently ethylene or propylene, R.sup.3 is hydrogen or
methyl, and the sum of x and y is an average number from about 2 to
about 20. Even more preferably, R.sup.1 is a linear or branched
alkyl group having from about 8 to about 22 carbon atoms and
R.sup.4 is a linear or branched alkyl group having from 1 to about
22 carbon atoms, R.sup.2 in each of the x (R.sup.2O) and y
(R.sup.2O) groups is independently ethylene or propylene, R.sup.3
is hydrogen or methyl, and the sum of x and y is an average number
from about 2 to about 20. Most preferably, R.sup.1 is a linear or
branched alkyl group having from about 8 to about 22 carbon atoms
and R.sup.4 is a linear or branched alkyl group having from 1 to
about 6 carbon atoms, R.sup.2 in each of the x (R.sup.2O) and y
(R.sup.2O) groups is independently ethylene or propylene, R.sup.3
is hydrogen or methyl, and the sum of x and y is an average number
from about 2 to about 15, or R.sup.1 and R.sup.4 are independently
a linear or branched alkyl group having from about 8 to about 22
carbon atoms, R.sup.2 in each of the x (R.sup.2O) and y (R.sup.2O)
groups is independently ethylene or propylene, R.sup.3 is hydrogen
or methyl, and the sum of x and y is an average number from about 5
to about 15. Preferred dialkoxylated quaternary ammonium
surfactants include Ethoquad.TM. C12 (a PEG 2 coco methyl ammonium
chloride from Akzo Nobel), PEG 5 coco methyl ammonium chloride, PEG
5 tallow methyl ammonium chloride, PEG 5 ditallow ammonium bromide,
and PEG 10 ditallow ammonium bromide.
[0089] (d) a monoalkoxylated quaternary ammonium salt having the
formula: 4
[0090] wherein R.sup.1 and R.sup.5 are independently hydrogen or
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, R.sup.4 is hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, R.sup.2 in each of the x
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, or a linear or branched alkyl group having
from 1 to about 30 carbon atoms, x is an average number from 1 to
about 60, and X- is an agriculturally acceptable anion. In this
context, preferred R.sup.1, R.sup.4, and R.sup.5 hydrocarbyl groups
are linear or branched alkyl, linear or branched alkenyl, linear or
branched alkynyl, aryl, or aralkyl groups. Preferably, R.sup.1,
R.sup.4 and R.sup.5 are independently a linear or branched alkyl or
linear or branched alkenyl group having from 1 to about 25 carbon
atoms, R.sup.2 in each of the x (R.sup.2O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, methyl or ethyl, and
x is an average number from 1 to about 40. More preferably,
R.sup.1, R.sup.4 and R.sup.5 are independently a linear or branched
alkyl group having from 1 to about 22 carbon atoms, R.sup.2 in each
of the x (R.sup.2O) groups is independently ethylene or propylene,
R.sup.3 is hydrogen or methyl, and x is an average number from 1 to
about 30. Even more preferably, R.sup.1 is a linear or branched
alkyl group having from about 8 to about 22 carbon atoms, R.sup.2
in each of the x (R.sup.2O) groups is independently ethylene or
propylene, R.sup.3 is hydrogen or methyl, R.sup.4 and R.sup.5 are
independently a linear or branched alkyl group having from 1 to
about 22 carbon atoms, and x is an average number from 1 to about
30. Even more preferably, R.sup.1 is a linear or branched alkyl
group having from about 8 to about 22 carbon atoms, R.sup.2 in each
of the x (R.sup.2O) groups is independently ethylene or propylene,
R.sup.3 is hydrogen or methyl, R.sup.4 and R.sup.5 are
independently a linear or branched alkyl group having from 1 to
about 6 carbon atoms, and x is an average number from about 5 to
about 25. Most preferably, R.sup.1 is a linear or branched alkyl
group having from about 16 to about 22 carbon atoms, R.sup.2 in
each of the x (R.sup.2O) groups is independently ethylene or
propylene, R.sup.3 is hydrogen or methyl, R.sup.4 and R.sup.5 are
independently a linear or branched alkyl group having from 1 to
about 3 carbon atoms, and x is an average number from about 5 to
about 25. Preferred monoalkoxylated quaternary ammonium surfactants
include PEG 7 C.sub.18 dimethyl ammonium chloride and PEG 22
C.sub.18 dimethyl ammonium chloride.
[0091] (e) a quaternary ammonium salt having the formula: 5
[0092] wherein R.sup.1, R.sup.3 and R.sup.4 are independently
hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to
about 30 carbon atoms, R.sup.2 is hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, and X- is an
agriculturally acceptable anion. In this context, preferred
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 hydrocarbyl groups are
linear or branched alkyl, linear or branched alkenyl, linear or
branched alkynyl, aryl, or aralkyl groups. Preferably, R.sup.1 is a
linear or branched alkyl or linear or branched alkenyl group having
from about 8 to about 30 carbon atoms, and R.sup.2,, R.sup.3 and
R.sup.4 are independently a linear or branched alkyl or linear or
branched alkenyl group having from 1 to about 30 carbon atoms. More
preferably, R.sup.1 is a linear or branched alkyl or linear or
branched alkenyl group having from about 8 to about 22 carbon
atoms, and R.sup.2, R.sup.3 and R.sup.4 are independently a linear
or branched alkyl or linear or branched alkenyl group having from 1
to about 6 carbon atoms. Even more preferably, R.sup.1 is a linear
or branched alkyl group having from about 8 to about 16 carbon
atoms, and R.sup.2,, R.sup.3 and R.sup.4 are independently a linear
or branched alkyl group having from 1 to about 6 carbon atoms. Most
preferably, R.sup.1 is a linear or branched alkyl group having from
about 8 to about 14 carbon atoms, and R.sup.2,, R.sup.3 and R.sup.4
are methyl. Preferred commercially available quaternary ammonium
surfactants include Arquad.TM. C-50 (a dodecyl trimethyl ammonium
chloride from Akzo Nobel) and Arquad.TM. T-50 (a tallow trimethyl
ammonium chloride from Akzo Nobel).
[0093] (f) an ether amine having the formula: 6
[0094] wherein R.sup.1 is hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms; R.sup.2 is hydrocarbylene
or substituted hydrocarbylene having from 2 to about 30 carbon
atoms; R.sup.3 and R.sup.4 are independently hydrogen, hydrocarbyl
or substituted hydrocarbyl having from 1 to about 30 carbon atoms,
or --(R.sup.5O).sub.xR.sup.6, R.sup.5 in each of the x(R.sup.5--O)
groups is independently C.sub.2-C.sub.4 alkylene, R.sup.6 is
hydrogen, or a linear or branched alkyl group having from 1 to
about 4 carbon atoms, and x is an average number from 1 to about
50. In this context, preferred R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 hydrocarbyl (hydrocarbylene) groups are linear or branched
alkyl (alkylene), linear or branched alkenyl (alkenylene), linear
or branched alkynyl (alkynylene), aryl (arylene), or aralkyl
(aralkylene) groups. Preferably, R.sup.1 is a linear or branched
alkyl, linear or branched alkenyl, linear or branched alkynyl,
aryl, or aralkyl group having from 8 to about 25 carbon atoms,
R.sup.2 is a linear or branched alkylene or alkenylene group having
from 2 to about 30 carbon atoms, R.sup.3 and R.sup.4 are
independently hydrogen, a linear or branched alkyl, linear or
branched alkenyl, linear or branched alkynyl, aryl, or aralkyl
group having from 1 to about 30 carbon atoms, or
--(R.sup.5O).sub.xR.sup.6, R.sup.5 in each of the x (R.sup.5O)
groups is independently C.sub.2-C.sub.4 alkylene, R.sup.6 is
hydrogen, methyl or ethyl, and x is an average number from 1 to
about 30. More preferably, R.sup.1 is a linear or branched alkyl or
alkenyl group having from 8 to about 22 carbon atoms, R.sup.2 is a
linear or branched alkylene or alkenylene group having from 2 to
about 6 carbon atoms, R.sup.3 and R.sup.4 are independently
hydrogen, a linear or branched alkyl or alkenyl group having from 1
to about 6 carbon atoms, or --(R.sup.5O).sub.xR.sup.6- , R.sup.5 in
each of the x (R.sup.5O) groups is independently ethylene or
propylene, R.sup.6 is hydrogen or methyl, and x is an average
number from 1 to about 15. Most preferably, R.sup.1 is a linear or
branched alkyl or alkenyl group having from 8 to about 18 carbon
atoms, R.sup.2 is ethylene or propylene, R.sup.3 and R.sup.4 are
independently hydrogen, methyl, or --(R.sup.5O).sub.xR.sup.6,
R.sup.5 in each of the x (R.sup.5O) groups is independently
ethylene or propylene, R.sup.6 is hydrogen, and x is an average
number from 1 to about 5.
[0095] (g) a diamine having the formula: 7
[0096] wherein R.sup.1, R.sup.3, R.sup.4 and R.sup.5 are
independently hydrogen, hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, or
--(R.sup.6O).sub.xR.sup.7; R.sup.2 and R.sup.8 are independently
hydrocarbylene or substituted hydrocarbylene having from 2 to about
30 carbon atoms, R.sup.6 in each of the x (R.sup.6O) and y
(R.sup.6O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.7 is hydrogen, or a linear or branched alkyl group having
from 1 to about 30 carbon atoms, x is an average number from 1 to
about 30, X is --O--, --N(R.sup.6)--, --C(O)--, --C(O)O--,
--OC(O)--, --N(R.sup.9)C(O)--, --C(O)N(R.sup.9)--, --S--, --SO--,
or --SO.sub.2--, y is 0 or an average number from 1 to about 30, n
and z are independently 0 or 1, and R.sup.9 is hydrogen or
hydrocarbyl or substituted hydrocarbyl. In this context, preferred
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.9 hydrocarbyl
(hydrocarbylene) groups are linear or branched alkyl (alkylene),
linear or branched alkenyl (alkenylene), linear or branched alkynyl
(alkynylene), aryl (arylene), or aralkyl (aralkylene) groups.
Preferably, R.sup.1 and R.sup.4 are independently a linear or
branched alkyl or linear or branched alkenyl group having from
about 1 to about 22 carbon atoms, R.sup.2 and R.sup.8 are
independently linear or branched alkylene groups having from about
2 to about 25 carbon atoms, R.sup.3 and R.sup.5 are each
independently hydrogen or a linear or branched alkyl group having
from 1 to about 6 carbon atoms and n, y and z are 0; or R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 are independently hydrogen or a linear
or branched alkyl or alkenyl group having from about 1 to about 6
carbon atoms, R.sup.2 is a linear or branched alkylene or
alkenylene group having from about 8 to about 25 carbon atoms, and
n, y and z are 0; or R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
independently hydrogen or a linear or branched alkyl or alkenyl
group having from about 1 to about 6 carbon atoms, R.sup.2 is a
linear or branched alkylene or alkenylene group having from about 1
to about 6 carbon atoms, R.sup.6 in each of the y (R.sup.6O) groups
is independently C.sub.2-C.sub.4 alkylene, y is an average number
from 1 to about 20 and n and z are 0; or R.sup.1 and R.sup.3 are
independently a linear or branched alkyl or linear or branched
alkenyl group having from about 8 to about 22 carbon atoms,
R.sup.2is a linear or branched alkylene group having from about 2
to about 25 carbon atoms; and R.sup.4 and R.sup.5 are each
independently hydrogen, a linear or branched alkyl or alkenyl group
having from 1 to about 6 carbon atoms, or
--(R.sup.6O).sub.xR.sup.7, R.sup.6 in each of the x (R.sup.6O)
groups is independently C.sub.2-C.sub.4 alkylene, R.sup.7 is
hydrogen, or a linear or branched alkyl group having from 1 to
about 4 carbon atoms, x is an average number from 1 to about 30,
and n, y and z are 0; or R.sup.1 is a linear or branched alkyl or
linear or branched alkenyl group having from about 1 to about 22
carbon atoms, R.sup.2 is a linear or branched alkylene group having
from about 2 to about 25 carbon atoms, R.sup.3, R.sup.4 and R.sup.5
are each independently hydrogen or a linear or branched alkyl group
having from 1 to about 6 carbon atoms, X is --C(O)-- is
--SO.sub.2--, n and y are 0 and z is 1. More preferably, R.sup.1
and R.sup.4 are independently a linear or branched alkyl or linear
or branched alkenyl group having from about 4 to about 18 carbon
atoms, R.sup.2 is a linear or branched alkylene group having from
about 2 to about 6 carbon atoms, R.sup.3 and R.sup.5 are each
independently hydrogen or a linear or branched alkyl group having
from 1 to about 6 carbon atoms, and n, y and z are 0; or R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 are independently hydrogen or a linear
or branched alkyl group having from about 1 to about 6 carbon
atoms, R.sup.2 is a linear or branched alkylene group having from
about 8 to about 25 carbon atoms, and y is 0; or R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 are independently hydrogen or a linear or
branched alkyl group having from about 1 to about 6 carbon atoms,
R.sup.2 is a linear or branched alkylene group having from about 1
to about 6 carbon atoms, R.sup.6 in each of the y (R.sup.6O) groups
is independently ethylene or propylene, y is an average number from
1 to about 10 and n and z is 0; or R.sup.1 and R.sup.3 are
independently a linear or branched alkyl group having from about 8
to about 22 carbon atoms, R.sup.2 is a linear or branched alkylene
group having from about 2 to about 6 carbon atoms, and R.sup.4 and
R.sup.5 are each independently hydrogen, a linear or branched alkyl
group having from 1 to about 6 carbon atoms, or
--(R.sup.6O).sub.xR.sup.7- , R.sup.6 in each of the x (R.sup.6O)
groups is independently ethylene or propylene, R.sup.7 is hydrogen
or methyl, x is an average number from 1 to about 15, and n, y and
z are 0; or R.sup.1 is a linear or branched alkyl group having from
about 1 to about 22 carbon atoms, R.sup.2 is a linear or branched
alkylene group having from about 2 to about 6 carbon atoms,
R.sup.3, R.sup.4 and R.sup.5 are each independently hydrogen, X is
--C(O)-- is --SO.sub.2--, n and y are 0 and z is 1. Preferred
diamines include Gemini 14-2-14, Gemini 14-3-14, Gemini 10-2-10,
Gemini 10-3-10, Gemini 10-4-10, and Gemini 16-2-16 (C.sub.10,
C.sub.14 or C.sub.16 ethylene, propylene or butylene N-methyl
diamines from Monsanto), Ethoduomeens.TM., and Jeffamine.TM.
EDR-148.
[0097] (h) an amine oxide having the formula: 8
[0098] wherein R.sup.1, R.sup.2 and R.sup.3 are independently
hydrogen, hydrocarbyl or substituted hydrocarbyl,
--(R.sup.4O).sub.xR.sup.5, or --R.sup.6(OR.sup.4).sub.xOR.sup.5;
R.sup.4 in each of the x (R.sup.4O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.5 is hydrogen, or a linear or
branched alkyl group having from 1 to about 30 carbon atoms,
R.sup.6 is hydrocarbylene or substituted hydrocarbylene having from
2 to about 6 carbon atoms, x in each of the x (R.sup.4O) groups is
independently an average number from 1 to about 50, and the total
number of carbon atoms in R.sup.1, R.sup.2 and R.sup.3 is at least
8. In this context, preferred R.sup.1, R.sup.2, R.sup.3, and
R.sup.6 hydrocarbyl (hydrocarbylene) groups are linear or branched
alkyl (alkylene), linear or branched alkenyl (alkenylene), linear
or branched alkynyl (alkynylene), aryl (arylene), or aralkyl
(aralkylene) groups. Preferably, R.sup.1 and R.sup.2 are
independently hydrogen, a linear or branched alkyl or linear or
branched alkenyl group having from 1 to about 30 carbon atoms, or
--(R.sup.4O).sub.xR.sup.5; R.sup.3 is a linear or branched alkyl or
linear or branched alkenyl group having from about 8 to about 30
carbon atoms, R.sup.4 in each of the x (R.sup.4O) groups is
independently C.sub.2-C.sub.4 alkylene; R.sup.5 is hydrogen, methyl
or ethyl, and x is an average number from 1 to about 30. More
preferably, R.sup.1 and R.sup.2 are independently hydrogen, or a
linear or branched alkyl group having from 1 to about 6 carbon
atoms, and R.sup.3 is a linear or branched alkyl group having from
about 8 to about 22 carbon atoms; or R.sup.1 and R.sup.2 are
independently --(R.sup.4O).sub.xR.sup.5- , R.sup.3 is a linear or
branched alkyl group having from about 8 to about 22 carbon atoms,
R.sup.4 in each of the x (R.sup.4O) groups is ethylene or
propylene, R.sup.5 is hydrogen or methyl, and x is an average
number from 1 to about 10. Most preferably, R.sup.1 and R.sup.2 are
independently methyl, and R.sup.3is a linear or branched alkyl
group having from about 8 to about 18 carbon atoms; or R.sup.1 and
R.sup.2 are independently --(R.sup.4O).sub.xR.sup.5, R.sup.3 is a
linear or branched alkyl group having from about 8 to about 18
carbon atoms, R.sup.4 in each of the x (R.sup.4O) groups is
ethylene or propylene, R.sup.5is hydrogen, and x is an average
number from 1 to about 5. Commercially available amine oxide
surfactants include Chemoxide L70.
[0099] (i) a dialkoxylated amine having the formula: 9
[0100] wherein R.sup.1 is a hydrocarbyl or substituted hydrocarbyl
having from about 6 to about 30 carbon atoms, or --R.sup.4SR.sup.5,
R.sup.4 and R.sup.2 in each of the x (R.sup.2O) and the y
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, or a linear or branched alkyl group having
from 1 to about 4 carbon atoms, R.sup.5 is a linear or branched
alkyl group having from about 4 to about 15 carbon atoms, and x and
y are independently an average number from 1 to about 40. In this
context, preferred R.sup.1 hydrocarbyl groups are linear or
branched alkyl, linear or branched alkenyl, linear or branched
alkynyl, aryl, or aralkyl groups. Preferably, R.sup.1 is a linear
or branched alkynyl, aryl, or aralkyl group having from about 8 to
about 30 carbon atoms, R.sup.2 in each of the x (R.sup.2O) and the
y (R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, methyl or ethyl, and x and y are independently
an average number from 1 to about 20. More preferably, R.sup.1 is a
linear or branched alkynyl, aryl, or aralkyl group having from
about 8 to about 25 carbon atoms, R.sup.2 in each of the x
(R.sup.2O) and the y (R.sup.2O) groups is independently ethylene or
propylene, R.sup.3 is hydrogen or methyl, and x and y are
independently an average number from 1 to about 30. Even more
preferably, R.sup.1 is a linear or branched alkynyl, aryl, or
aralkyl group having from about 8 to about 22, or about 12 to about
22, carbon atoms, R.sup.2 in each of the x (R.sup.2O) and the y
(R.sup.2O) groups is independently ethylene or propylene, R.sup.3is
hydrogen or methyl, and x and y are independently an average number
from 1 to about 5. Some commercially available dialkoxylated amines
include, for example, Trymeen.TM. 6617 (from Cognis) and
Ethomeen.TM. C/12, C/15, C/20, C/25, T/12, T/15, T/20 and T/25
(from Akzo Nobel).
[0101] and (j) an aminated alkoxylated alcohol having the formula:
10
[0102] wherein R.sup.1, R.sup.7, R.sup.8, and R.sup.9are each
independently hydrogen, hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, or
--(R.sup.11).sub.s(R.sup.3O).sub.vR.s- up.10; X is --O--,
--OC(O)--, --C(O)O--, --N(R.sup.12)C(O)--, --C(O)N(R.sup.12)--,
--S--, --SO--, --SO.sub.2-- or --N(R.sup.9)--; R.sup.3 in each of
the n (R.sup.3O) groups and the v (R.sup.3O) groups is
independently C.sub.2-C.sub.4 alkylene; R.sup.10 is hydrogen, or a
linear or branched alkyl group having from 1 to about 30 carbon
atoms; n is an average number from 1 to about 60; v is an average
number from 1 to about 50; R.sup.2 and R.sup.11 are each
independently hydrocarbylene or substituted hydrocarbylene having
from 1 to about 6 carbon atoms; R.sup.4 is hydrocarbylene or
substituted hydrocarbylene having from 2 to about 6 carbon atoms;
R.sup.12 is hydrogen or hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms; m and s are each
independently 0 or 1; R.sup.6 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 30 carbon atoms,
--C(.dbd.NR.sup.12)--, --C(S)--, or --C(O)--; q is an integer from
0 to 5; and R.sup.5 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms. In this
context, preferred R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, R.sup.8, R.sup.9, R.sup.11 and R.sup.12 hydrocarbyl
(hydrocarbylene) groups are linear or branched alkyl (alkylene),
linear or branched alkenyl (alkenylene), linear or branched alkynyl
(alkynylene), aryl (arylene), or aralkyl (aralkylene) groups.
[0103] A subclass of such cationic surfactants includes
monoalkoxylated amines having the formula: 11
[0104] wherein R.sup.1 is hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms; R.sup.2 in each
of the x (R.sup.2O) and y (R.sup.2O) groups is independently
C.sub.2-C.sub.4 alkylene; R.sup.3 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 30 carbon atoms; R.sup.4 and
R.sup.5 are each independently hydrogen, hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms,
--(R.sup.6).sub.n--(R.sup.2O).sub.yR.sup- .7, or R.sup.4 and
R.sup.5, together with the nitrogen atom to which they are
attached, form a cyclic or heterocyclic ring; R.sup.6 is
hydrocarbylene or substituted hydrocarbylene having from 1 to about
30 carbon atoms; R.sup.7 is hydrogen or a linear or branched alkyl
group having 1 to about 4 carbon atoms, n is 0 or 1, x and y are
independently an average number from 1 to about 60. In this
context, preferred R.sup.1, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
hydrocarbyl (hydrocarbylene) groups are linear or branched alkyl
(alkylene), linear or branched alkenyl (alkenylene), linear or
branched alkynyl (alkynylene), aryl (arylene), or aralkyl
(aralkylene) groups. Preferably, R.sup.1 is a linear or branched
alkyl or linear or branched alkenyl group having from about 8 to
about 25 carbon atoms, R.sup.2 in each of the x (R.sup.2O) groups
is independently C.sub.2-C.sub.4 alkylene, R.sup.3 is a linear or
branched alkylene group having from 2 to about 20 carbon atoms,
R.sup.4 and R.sup.5 are each independently hydrogen or a linear or
branched alkyl group having from 1 to about 6 carbon atoms, and x
is an average number from 1 to about 30. More preferably, R.sup.1
is a linear or branched alkyl group having from about 12 to about
22 carbon atoms, R.sup.2 in each of the x (R.sup.2O) groups is
independently ethylene or propylene, R.sup.3 is a linear or
branched alkylene group having from 2 to about 6 carbon atoms,
R.sup.4 and R.sup.5 are each independently hydrogen, methyl, or
tris(hydroxymethyl)methyl, and x is an average number from about 2
to about 30. Even more preferably, R.sup.1 is a linear or branched
alkyl group having from about 12 to about 18 carbon atoms, R.sup.2
in each of the x (R.sup.2O) groups is independently ethylene or
propylene, R.sup.3 is ethylene or propylene, R.sup.4 and R.sup.5
are each independently hydrogen, methyl or
tris(hydroxymethyl)methyl, and x is an average number from about 4
to about 20. Most preferably, R.sup.1 is a linear or branched alkyl
group having from about 12 to about 18 carbon atoms, R.sup.2 in
each of the x (R.sup.2O) groups is independently ethylene or
propylene, R.sup.3 is ethylene, R.sup.4 and R.sup.5 are methyl, and
x is an average number from about 4 to about 20. Preferred
monoalkoxylated amines include PEG 13 or 18 C.sub.14-15 ether
propylamines and PEG 7, 10, 15 or 20 C.sub.16-18 ether propylamines
(from Tomah) and PEG 13 or 18 C.sub.14-15 ether dimethyl
propylamines and PEG 10, 15 or 20 or 25 C.sub.16-18 ether dimethyl
propylamines (from Tomah) and Surfonic.TM. AGM-550 from
Huntsman.
[0105] Quaternary ammonium, sulfonium and sulfoxonium salts are
also effective cationic surfactants in forming glyphosate
concentrates and have the chemical structures: 12
[0106] wherein R.sup.1, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and
R.sup.11 are independently hydrogen, hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, or
--(R.sup.13).sub.s(R.sup.3).sub.vR.su- p.12; X is --O--, --OC(O)--,
--N(R.sup.14)C(O)--, --C(O)N(R.sup.14)--, --C(O)O--, or --S--;
R.sup.3 in each of the n (R.sup.3O) groups and v (R.sup.3O) groups
is independently C.sub.2-C.sub.4 alkylene; R.sup.12 is hydrogen, or
a linear or branched alkyl group having from 1 to about 30 carbon
atoms; n is an average number from 1 to about 60; v is an average
number from 1 to about 50; R.sup.2 and R.sup.13 are each
independently hydrocarbylene or substituted hydrocarbylene having
from 1 to about 6 carbon atoms; m and s are each independently 0 or
1; R.sup.4 is hydrocarbylene or substituted hydrocarbylene having
from 2 to about 6 carbon atoms; R.sup.6 is hydrocarbylene or
substituted hydrocarbylene having from 2 to about 30 carbon atoms,
--C(.dbd.NR.sup.12)--, --C(S)--, or --C(O)--; R.sup.14 is hydrogen
or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms, q is an integer from 0 to 5; R.sup.5 is hydrogen or
hydrocarbyl or substituted hydrocarbyl having from 1 to about 30
carbon atoms; and each A.sup.- is an agriculturally acceptable
anion. In this context, preferred R.sup.1, R.sup.2, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11,
R.sup.13, and R.sup.14 hydrocarbyl (hydrocarbylene) groups are
linear or branched alkyl (alkylene), linear or branched alkenyl
(alkenylene), linear or branched alkynyl (alkynylene), aryl
(arylene), or aralkyl (aralkylene) groups.
[0107] Other cationic surfactants effective in any glyphosate
composition or formulation are diamines or diammonium salts having
the formulas: 13
[0108] wherein R.sup.1, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and
R.sup.8 are independently hydrogen or hydrocarbyl or substituted
hydrocarbyl having from 1 to about 30 carbon atoms, R.sup.2 in each
of the m (R.sup.2O) and n (R.sup.2O) groups and R.sup.9 are
independently C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrocarbylene
or substituted hydrocarbylene having from about 2 to about 6 carbon
atoms or --(R.sup.2O).sub.pR.sub.9--, m and n are individually an
average number from 0 to about 50, and p is an average number from
0 to about 60. In this context, preferred R.sup.1, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 hydrocarbyl
(hydrocarbylene) groups are linear or branched alkyl (alkylene),
linear or branched alkenyl (alkenylene), linear or branched alkynyl
(alkynylene), aryl (arylene), or aralkyl (aralkylene) groups. In
one embodiment of formula (DA), R.sup.3 is hydrocarbylene having
from about 2 to about 6 carbon atoms, and the remaining groups are
as defined above.
[0109] Preferred nonionic surfactants for such glyphosate
concentrates include alkoxylated alcohols having the formula:
R.sup.1O--(R.sup.2O).sub.xR.sup.3 (18)
[0110] wherein R.sup.1 is hydrocarbyl or substituted hydrocarbyl
having from 1 to about 30 carbon atoms, R.sup.2 in each of the x
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, or a linear or branched alkyl group having
from 1 to about 4 carbon atoms, and x is an average number from 1
to about 60. In this context, preferred R.sup.1 hydrocarbyl groups
are linear or branched alkyl, linear or branched alkenyl, linear or
branched alkynyl, aryl, or aralkyl groups. Preferably, R.sup.1 is a
linear or branched alkyl or linear or branched alkenyl group having
from about 8 to about 30 carbon atoms, R.sup.2 in each of the x
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, methyl or ethyl, and x is an average number
from about 5 to about 50. More preferably, R.sup.1 is a linear or
branched alkyl group having from about 8 to about 25 carbon atoms,
R.sup.2 in each of the x (R.sup.2O) groups is independently
ethylene or propylene, R.sup.3 is hydrogen or methyl, and x is an
average number from about 8 to about 40. Even more preferably,
R.sup.1 is a linear or branched alkyl group having from about 12 to
about 22 carbon atoms, R.sup.2 in each of the x (R.sup.2O) groups
is independently ethylene or propylene, R.sup.3 is hydrogen or
methyl, and x is an average number from about 8 to about 30.
Preferred commercially available alkoxylated alcohols include
Procol.TM. LA-15 (from Protameen), Brij.TM. 35, Brij.TM. 76,
Brij.TM. 78, Brij.TM. 97 and Brij.TM. 98 (from Sigma Chemical Co.),
Neodol.TM. 25-12 (from Shell), Hexotol.TM. CA-10, Hexotol.TM.
CA-20, Hexotol.TM. CS-9, Hexotol.TM. CS-15, Hexotol.TM. CS-20,
Hexotol.TM. CS-25, Hexotol.TM. CS-30, and Plurafac.TM. A38 (from
BASF), ST-8303 (from Cognis), and Arosurf.TM. 66 E20 (from
Witco/Crompton).
[0111] Other nonionic surfactants for use in such glyphosate
compositions or formulations include alkoxylated dialkylphenols
having the formula: 14
[0112] wherein R.sup.1 and R.sup.4 are independently hydrogen, or a
linear or branched alkyl group having from 1 to about 30 carbon
atoms and at least one of R.sup.1 and R.sup.4 is an alkyl group,
R.sup.2 in each of the x (R.sup.2O) groups is independently
C.sub.2-C.sub.4 alkylene, R.sup.3 is hydrogen, or a linear or
branched alkyl group having from 1 to about 4 carbon atoms, and x
is an average number from 1 to about 60. Preferably, R.sup.1 and
R.sup.4 are independently linear or branched alkyl groups having
from 8 to about 30 carbon atoms, R.sup.2 in each of the x
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene,
R.sup.3 is hydrogen, methyl or ethyl, and x is an average number
from about 5 to about 50. More preferably, R.sup.1 and R.sup.4 are
independently linear or branched alkyl groups having from about 8
to about 22 carbon atoms, R.sup.2 in each of the x (R.sup.2O)
groups is independently ethylene or propylene, R.sup.3is hydrogen
or methyl, and x is an average number from about 8 to about 40.
Even more preferably, R.sup.1 and R.sup.4 are independently linear
or branched alkyl groups having from about 8 to about 16 carbon
atoms, R.sup.2 in each of the x (R.sup.2O) groups is independently
ethylene or propylene, R.sup.3is hydrogen or methyl, and x is an
average number from about 10 to about 30. Preferred commercially
available alkoxylated dialkylphenols include ethoxylated dinonyl
phenols such as Surfonic.TM. DNP 100, Surfonic.TM. DNP 140, and
Surfonic.TM. DNP 240 (from Huntsman).
[0113] Preferred anionic surfactants effective in forming
glyphosate compositions or formulations, in at least some
embodiments, may include saturated carboxylic acids such as
butyric, caproic, caprylic, capric, lauric, palmitic, myristic or
stearic acid, and unsaturated carboxylic acids such as palmitoleic,
oleic, linoleic or linolenic acid. Preferred carboxylic acids, in
at least some embodiments, may include palmitic, oleic or stearic
acid. Other preferred anionic surfactants, in at least some
embodiments, may include alkyl sulfates such as sodium lauryl
sulfate, and alkyl alkoxylated phosphates having the formulae:
15
[0114] wherein R.sup.1 and R.sup.3 are independently a linear or
branched alkyl, linear or branched alkenyl, linear or branched
alkynyl, aryl, or aralkyl group having from about 4 to about 30
carbon atoms; R.sup.2 in each of the m (R.sup.2O) and the n
(R.sup.2O) groups is independently C.sub.2-C.sub.4 alkylene; and m
and n are independently from 1 to about 30; or 16
[0115] wherein R.sup.1 is a linear or branched alkyl, linear or
branched alkenyl, linear or branched alkynyl, aryl, or aralkyl
group having from about 8 to about 30 carbon atoms; R.sup.2 in each
of the m (R.sup.2O) groups is independently C.sub.2-C.sub.4
alkylene; and m is from 1 to about 30. Representative alkyl
alkoxylated phosphates include oleth-10 phosphate, oleth-20
phosphate and oleth-25 phosphate. Other representative alkyl
alkoxylated phosphates include those wherein, in (21), R.sup.1 has
about 10 to about 15 carbon atoms, R.sup.2 is ethylene or
propylene, and m is from about 1 to about 10, from about 2 to about
8, or about 4 to about 6.
[0116] Other exemplary surfactants that may be used in accordance
with the present invention include the following species: 17
[0117] In at least some embodiments of one or more of the aqueous
or dry concentrates, or alternatively the ready-to-use composition,
described herein, the weight ratio of glyphosate (a.e. basis) to
surfactant may range from about 1:10 to 10:1 or more (e.g., from
about 1:8 to 8:1, from about 1:6 to about 6:1, from about 1:4 to
about 4:1, from about 1:3 to about 3:1, or from about 1:2 to about
2:1). Alternatively, this ratio may range from about 1:1 to about
10:1 (e.g., from about 1:1 to about 10:1, from about 2:1 to about
8:1, or from about 3:1 to about 6:1), from about 1:1 to about 15:1,
from about 1:1 to about 20:1, or more. Accordingly, exemplary
ratios include about 1:10, about 1:9.5, about 1:9, about 1:8.5,
about 1:8, about 1:7.5, about 1:7, about 1:6.5, about 1:6, about
1:5.5, about 1:5, about 1:4.5, about 1:4, about 1:3.5, about 1:3,
about 12.5, about 1:2, about 1:1.5, about 1:1, about 1.5:1, about
2:1, about 2.5:1, about 3:1, about 3.5:1, about 4:1, about 4.5:1,
about 5:1, about 5.5:1, about 6:1, about 6.5:1, about 7:1, about
7.5:1, about 8:1, about 8.5:1, about 9:1, about 9.5:1, about 10:1,
about 11:1, about 12:1, about 13:1, about 14:1, about 15:1, about
16:1, about 17:1, about 18:1, about 19:1, about 20:1 or more.
[0118] Alternatively, in these or other embodiments (e.g, a
ready-to-use composition), the weight ratio of glyphosate (a.e.
basis) to surfactant may range from about 10:1 to about 1:5 (e.g.,
from about 8:1 to about 1:4, from about 6:1 to about 1:3, from
about 4:1 to about 1:2, or from about 2:1 to about 1:1).
[0119] Additionally, in these or other embodiments, the surfactant
concentration may be at least about 1 gram per liter (e.g., at
least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150,
200, 250, 300, 350, 400, 450, 500 grams per liter or more), ranging
for example from about 1 to about 500 grams per liter, from about 5
to about 250 grams per liter, 10 to about 100 grams per liter, from
about 20 to about 80 grams per liter, or from about 40 to about 60
grams per liter. Alternatively, the surfactant concentration may
range from about 1 to 283 grams per liter (e.g., ranging for
example from about 1 to about 275 grams per liter, from about 5 to
about 250 grams per liter, from about 10 to about 100 grams per
liter, from about 20 to about 80 grams per liter, or from about 40
to about 60 grams per liter).
[0120] In some embodiments (e.g., a ready-to-use composition), the
surfactant concentration may not be greater than 3.9 grams per
liter (e.g., not greater than 3.8, 3.6, 3.4, 3.2, 3, 2.8, 2.6, 2.4,
2.2, 2, 1.8, 1.6, 1.4, 1.2, 1 or less), when the weight ratio (a.e.
to a.e.) of glyphosate to pyridine analog (triclopyr, for example)
is at least 3:1. In these or other embodiments, the surfactant
concentration may not be greater than 6.6 grams per liter (e.g.,
not greater than 6.4, 6.2, 6, 5.8, 5.6, 5.4, 5.2, 5, 4.8, 4.6, 4.4,
4.2, 4, 3.8, etc.), when the weight ratio (a.e. to a.e.) of
glyphosate to pyridine analog (triclopyr, for example) is at least
5:1. In these or still other embodiments, the surfactant
concentration may not be greater than 9.3 grams per liter (e.g.,
not greater than 9.2, 9. 8.8, 8.6, 8.4, 8.2, 8, 7.8, 7.6, 7.4, 7.2,
7, 6.8, 6.6, 6.4, etc.), when the weight ratio (a.e. to a.e.) of
glyphosate to pyridine analog (triclopyr, for example) is at least
7:1.
[0121] III. Properties
[0122] Among the various properties of the compositions of the
present invention is to be noted that these compositions typically
have a cloud point of at least about 50.degree. C., or even about
60.degree. C. Additionally, the aqueous concentrate and/or the
ready-to-use composition of the present invention typically has a
composition such that triclopyr (or more generally the pyridine
analog) will not crystallize or precipitate when the bulk solution
freezes or solidifies, and then thaws; stated another way, the
herbicide compositions or formulations of the present invention
have a composition wherein the pyridine analog, such as triclopyr,
will not precipitate upon being cooled to a temperature of about
0.degree. C., or even about -10.degree. C.
[0123] IV. Optional Additives
[0124] As further discussed herein, other additives, adjuvants, or
ingredients may be introduced into the compositions or formulations
of the present invention to improve certain properties thereof
(e.g., solubility of the pyridine analog). Although the
compositions or formulations of the present invention generally
show good overall stability and viscosity properties without the
addition of any further additives, the addition of a solubilizer
(also commonly referred to as a cloud point enhancer or stabilizer)
may significantly improve the properties of the compositions or
formulations of the present invention. Suitable solubilizers for
use with the novel compositions or formulations of the present
invention include, for example, cocoamine (Armeen C),
dimethylcocoamine (Arquad DMCD), cocoammonium chloride (Arquad C),
PEG 2 cocoamine (Ethomeen C12), a cocodiamine 3EO (Ethoduomeen
CD/13), PEG 5 tallowamine (Ethomeen T15), and PEG 5 cocoamine
(Ethomeen C15), all of which are manufactured by Akzo Nobel
(California).
[0125] Additionally, it has been found that the addition of a
C.sub.4 to C.sub.16 alkyl or aryl amine compound, or the
corresponding quaternary ammonium compound, greatly enhances the
compatibility of certain glyphosate salts (e.g., potassium or
isopropylamine) with surfactants that otherwise exhibit low or
marginal compatibility at a given glyphosate loading. Suitable
alkyl or aryl amine compounds may also contain 0 to about 5 EO
groups. Preferred alkylamine compounds include C.sub.6 to C.sub.12
alkylamines having 0 to 2 EO groups. Similarly, etheramine
compounds having 4 to 12 carbons and 0 to about 5 EO groups, as
well as the corresponding quaternary ammonium compounds, also
enhance the compatibility of such compositions or formulations. In
one embodiment, the compounds which enhance the compatibility of
such surfactants include amines or quaternary ammonium salts having
the formula: 18
[0126] wherein R.sup.1 is linear or branched alkyl or aryl having
from about 4 to about 16 carbon atoms, R.sup.2 is hydrogen, methyl,
ethyl, or --(CH.sub.2CH.sub.2O).sub.xH, R.sup.3 is hydrogen,
methyl, ethyl, or --(CH.sub.2CH.sub.2O).sub.yH wherein the sum of x
and y is not more than about 5; R.sup.4 is hydrogen or methyl;
R.sup.6 in each of the n (R.sup.6O) groups is independently
C.sub.2-C.sub.4 alkylene; R.sup.5 is hydrocarbylene or substituted
hydrocarbylene having from 2 to about 6 carbon atoms; and A- is an
agriculturally acceptable anion.
[0127] Optionally, one or more of the compositions of the present
invention may further comprise one or more additional pesticides,
such as for example, water-soluble herbicidal active ingredients,
including without restriction water-soluble forms of acifluorfen,
asulam, benazolin, bentazon, bialaphos, bispyribac, bromacil,
bromoxynil, carfentrazone, chloramben, 2,4-D, 2,4-DB, dalapon,
dicamba, dichlorprop, diclofop, difenzoquat, diquat, endothall,
fenac, fenoxaprop, flamprop, fluazifop, fluoroglycofen, fomesafen,
fosamine, glufosinate, haloxyfop, imazameth, imazamethabenz,
imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil,
MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid,
paraquat, sulfamic acid, 2,3,6-TBA, TCA, acetochlor, aclonifen,
alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin,
azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl,
bensulide, benzofenap, bifenox, bromobutide, bromofenoxim,
butachlor, butamifos, butralin, butroxydim, butylate, cafenstrole,
carbetamide, carfentrazone-ethyl, chlomethoxyfen, chlorbromuron,
chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron,
chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid,
cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl,
clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate,
cyclosulfamuron, cycloxydim, cyhalofop-butyl, daimuron,
desmedipham, desmetryn, dichlobenil, diclofop-methyl, diflufenican,
dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid,
dinitramine, dinoterb, diphenamid, diuron, EPTC, esprocarb,
ethalfluralin, ethametsulfuron-methyl, ethofumesate,
ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenuron,
flamprop-methyl, flazasulfuron, fluazifop-butyl, fluchloralin,
flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron,
fluorochloridone, fluoroglycofen-ethyl, flupoxam, flurenol,
fluridone, flurtamone, fluthiacet-methyl, fomesafen, halosulfuron,
haloxyfop-methyl, hexazinone, imazosulfuron, indanofan,
isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop,
lactofen, lenacil, linuron, mefenacet, metamitron, metazachlor,
methabenzthiazuron, methyidymron, metobenzuron, metobromuron,
metolachlor, metosulam, metoxuron, metribuzin, metsulfuron,
molinate, monolinuron, naproanilide, napropamide, naptalam,
neburon, nicosulfuron, norflurazon, orbencarb, oryzalin,
oxadiargyl, oxadiazon, oxasulfuron, oxyfluorfen, pebulate,
pendimethalin, pentanochlor, pentoxazone, phenmedipham, piperophos,
pretilachlor, primisulfuron, prodiamine, prometon, prometryn,
propachlor, propanil, propaquizafop, propazine, propham,
propisochlor, propyzamide, prosulfocarb, prosulfuron,
pyraflufen-ethyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen,
pyributicarb, pyridate, pyriminobac-methyl, quinclorac, quinmerac,
quizalofop-ethyl, rimsulfuron, sethoxydim, siduron, simazine,
simetryn, sulcotrione, sulfentrazone, sulfometuron, sulfosulfuron,
tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine,
terbutryn, thenylchlor, thifensulfuron, thiobencarb, tiocarbazil,
tralkoxydim, triallate, triasulfuron, tribenuron, trietazine,
trifluralin, triflusulfuron and vernolate.
[0128] Another ingredient that can optionally be added to the
glyphosate herbicidal compositions or formulations of the present
invention to further improve the herbicidal effectiveness and
related herbicidal properties is a di-carboxylic acid or salt of a
di-carboxylic acid. Suitable di-carboxylic acids that may be added
to the herbicidal compositions or formulations comprising
glyphosate or a salt or ester thereof and a surfactant as described
herein include, for example, oxalic acid, malonic acid, succinic
acid, glutaric acid, maleic acid, adipic acid, and fumaric acid,
and combinations or mixtures thereof, with oxalic acid being
preferred. Also, in addition to, or in place of the di-carboxylic
acid, salts of the aforementioned di-carboxylic acids may be
incorporated into the herbicidal formulations of the present
invention to improve herbicidal performance. Suitable salts
include, for example, alkali metal salts such as potassium salts,
alkanolamine salts and lower alkylamine salts. Preferred salts
include potassium oxalate, dipotassium oxalate, sodium oxalate,
disodium oxalate, diammonium oxalate, diethanolamine oxalate,
dimethylamine oxalate, alkanolamine salts of oxalic acid, and lower
alkylamine salts of oxalic acid.
[0129] Formulations containing a di-carboxylic acid such as oxalic
acid or a di-carboxylic acid salt such as potassium oxalate,
typically contain a sufficient amount of di-carboxylic
acid/di-carboxylic acid salt to enhance the resulting efficacy of
the herbicidal formulation. The weight ratio of total surfactant to
carboxylic acid/carboxylic acid salt may be, for example, from
about 1:1 to about 50:1, about 5:1 to about 40:1, or even about 5:1
to about 20:1. This ratio of total surfactant to carboxylic
acid/carboxylic acid salt may significantly enhance the herbicidal
performance of the resulting herbicidal formulation.
[0130] The di-carboxylic acid or salt thereof which can be added to
herbicidal formulations of the present invention to improve
efficacy are suitable for use with glyphosate, or salts thereof.
Suitable glyphosate salts include those listed above, such as for
example the isopropylamine salt, the potassium salt, and the
trimethylammonium salt.
[0131] In this regard it is to be noted that U.S. patent
application Ser. No. 09/988,353 (entitled Pesticide Compositions
Containing Oxalic Acid and published on Sep. 5, 2002 under
Publication No. US-2002-0123430-A1) is incorporated herein by
reference, as well as U.S. patent application Ser. No. 10/653,332
(entitled Process for the Preparation of a Dry Pesticidal
Composition Containing a Dicarboxylate Component and filed on Sep.
2, 2003) and U.S. patent application Ser. No. 10/653,047 (entitled
Pesticidal Compositions Containing Dicarboxylic Acids and filed on
Aug. 29, 2003).
[0132] Yet another ingredient that can optionally be added to one
or more of the compositions of the present invention is a fatty
acid (e.g., a C.sub.8 to C.sub.12 fatty acid). For example, in at
least one embodiment the present invention is directed to a
composition (e.g., a solid or liquid concentrate, or alternatively
a ready-to-use composition) comprising glyphosate (or a derivative
thereof), triclopyr or other pyridine analog (or a derivative
thereof), a pelargonic acid (or nonanoic acid) or derivative
thereof, and a surfactant, such as a linear alcohol ethoxylate.
[0133] Excipient ingredients other than the above-defined
surfactant component can optionally be present in a composition of
the invention, so long as the cloud point and non-crystallization
properties of the composition remain in accordance with the
invention. Such additional excipient ingredients may include
conventional formulation additives such as dyes, thickeners,
crystallization inhibitors, antifreeze agents (e.g., glycols, such
a ethylene glycol), foam moderating agents (e.g., Antifoam.TM. or
Y-14088 Antifoam.TM., both available from Crompton Corporation),
antidrift agents, compatibilizing agents, antioxidants (e.g.,
ascorbic acid and sodium sulfite, in order for example to prevent
the formation of a nitrosamine), other co-solvents (e.g.,
N-methylpyrrolidone, DMSO, DMF, propylene carbonate, or ethylene
glycol), or some other agent added to lessen or overcome antagonism
associated with hard water (e.g., ammonium sulfate, EDTA or a
polymeric water conditioner, such as a polyacrylic acid), etc.
[0134] V. Formulations
[0135] The herbicidal compositions of the invention can be prepared
on site by the end-user shortly before application to the foliage
of the vegetation to be killed or controlled by mixing in an
aqueous solution (i) glyphosate or a herbicidal derivative thereof,
(ii) a pyridine analog, such as triclopyr, or a derivative thereof,
and (iii) a suitable surfactant. Such compositions are typically
referred to as "tank-mix" compositions. Typically, herbicidal
compositions of the present invention that are ready to be applied
directly to foliage can be made with a glyphosate concentration as
described elsewhere herein. Additionally, such herbicidal
compositions can be made with a triclopyr, or some other pyridine
analog, at a concentration also as described elsewhere herein.
However, it is to be noted that one skilled in the art will
recognize that various factors influence the application rate of
glyphosate and, for example, triclopyr (or another pyridine
analog), required for a desired result. As a result, the
concentration of such compositions may be other than as described
herein without departing from the scope of the present
invention.
[0136] Alternatively, the herbicidal compositions of the invention
may be provided to the end-user already formulated, either at the
desired dilution for application (i.e., "ready-to-use"
compositions) or requiring dilution, dispersion, or dissolution in
water by the end-user (i.e., "concentrate" compositions, wherein
the glyphosate concentration is at least about 50 grams (a.e.) per
liter). Such preformulated concentrates can be liquids or
particulate solids.
[0137] With respect to the particulate solids, or dry formulations,
of the present invention, it is to be noted that these may be in
the form of powders, pellets, tablets or granules. These dry
formulations are typically dispersed or dissolved into water prior
to use. Preferably, there are no substantially water insoluble
constituents present at substantial levels in the such formulations
such that the formulations are substantially water soluble. Dry
water-soluble or water-dispersable formulations of the present
invention typically comprise the same ratios of glyphosate to
triclopyr (G:T), or more generally the same ratios of glyphosate to
pyridine analog, and glyphosate to surfactant (G:S), as described
elsewhere herein. With respect to the load of the composition
ingredients (i.e., glyphosate, triclopyr, or other pyridine analog,
and surfactant), as well as the particular ingredients themselves,
it is to be noted that the selection of these for a given
application may be determined in view of commercial consideration,
and using means, known in the art.
[0138] In dry formulations of the present invention, the glyphosate
itself may provide the support for other formulation constituents,
or there may be additional inert ingredients which provide such
support. One example of an inert support ingredient that may be
used in accordance with the present invention is ammonium sulfate.
It will be recognized by one skilled in the art that as used
herein, the term "dry" does not imply that dry formulations of the
present invention are 100% free of water. Typically, dry
formulations of the present invention comprise from about 0.5% to
about 5% (by weight) water. It is preferred that the dry
formulations of the present invention contain less than about 1%
(by weight) water. Additionally, it is preferred for at least some
embodiments that the particulate solid exhibits a dissolution rate
of not more than about 5 minutes, about 4 minutes, about 3 minutes,
about 2 minutes, or even about 1 minute.
[0139] Dry, water soluble or water dispersable formulations in
accordance with the present invention can be produced by any
process known in the art, including spray drying, fluid-bed
agglomeration, pan granulation, or extrusion. In dry formulations,
glyphosate may be present as a salt, or as an acid. Formulations
containing glyphosate acid may optionally contain an acid acceptor
such as an ammonium or alkali metal carbonate or bicarbonate,
ammonium dihydrogen phosphate or the like so that upon dissolution
or dispersion in water by the user a water soluble salt of
glyphosate is produced.
[0140] Also embraced by the present invention are liquid
concentrate formulations having an aqueous phase wherein glyphosate
is present predominantly in the form of a salt, and a non-aqueous
phase optionally containing a second herbicidal active ingredient
that is relatively water-insoluble. Such formulations
illustratively include emulsions (including macro- and
microemulsions, water-in-oil, oil-in-water and
water-in-oil-in-water types), suspensions and suspoemulsions. The
non-aqueous phase can optionally comprise a microencapsulated
component, for example a microencapsulated herbicide. In
formulations of the invention having a non-aqueous phase, the
concentration of glyphosate a.e. in the composition as a whole is
nonetheless within the ranges recited herein for aqueous
concentrate formulations.
[0141] Illustrative water-insoluble herbicides that can be used in
such formulations include acetochlor, aclonifen, alachlor, ametryn,
amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron,
benfluralin, benfuresate, bensulfuron-methyl, bensulide,
benzofenap, bifenox, bromobutide, bromofenoxim, butachlor,
butamifos, butralin, butroxydim, butylate, cafenstrole,
carbetamide, carfentrazone-ethyl, chlomethoxyfen, chlorbromuron,
chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron,
chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid,
cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl,
clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate,
cyclosulfamuron, cycloxydim, cyhalofop-butyl, daimuron,
desmedipham, desmetryn, dichlobenil, diclofop-methyl, diflufenican,
dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid,
dinitramine, dinoterb, diphenamid, diuron, EPTC, esprocarb,
ethalfluralin, ethametsulfuron-methyl, ethofumesate,
ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenuron,
flamprop-methyl, flazasulfuron, fluazifop-butyl, fluchloralin,
flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron,
fluorochloridone, fluoroglycofen-ethyl, flupoxam, flurenol,
fluridone, flurtamone, fluthiacet-methyl, fomesafen, halosulfuron,
haloxyfop-methyl, hexazinone, imazosulfuron, indanofan,
isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop,
lactofen, lenacil, linuron, mefenacet, metamitron, metazachlor,
methabenzthiazuron, methyidymron, metobenzuron, metobromuron,
metolachlor, metosulam, metoxuron, metribuzin, metsulfuron,
molinate, monolinuron, naproanilide, napropamide, naptalam,
neburon, nicosulfuron, norflurazon, orbencarb, oryzalin,
oxadiargyl, oxadiazon, oxasulfuron, oxyfluorfen, pebulate,
pendimethalin, pentanochlor, pentoxazone, phenmedipham, piperophos,
pretilachlor, primisulfuron, prodiamine, prometon, prometryn,
propachlor, propanil, propaquizafop, propazine, propham,
propisochlor, propyzamide, prosulfocarb, prosulfuron,
pyraflufen-ethyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen,
pyributicarb, pyridate, pyriminobac-methyl, quinclorac, quinmerac,
quizalofop-ethyl, rimsulfuron, sethoxydim, siduron, simazine,
simetryn, sulcotrione, sulfentrazone, sulfometuron, sulfosulfuron,
tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine,
terbutryn, thenylchlor, thifensulfuron, thiobencarb, tiocarbazil,
tralkoxydim, triallate, triasulfuron, tribenuron, trietazine,
trifluralin, triflusulfuron and vernolate.
[0142] It is to be noted that the herbicidal spray compositions of
the present invention are applied as aqueous solutions or
dispersions, whether they result from the further dilution of the
liquid concentrate or the addition of water to the particulate
solid concentrate. However, the term "aqueous," as used herein, is
not intended to exclude the presence of some small amount of
nonaqueous solvent, so long as the predominant solvent present,
other than for example the glycol or glycol ester component of the
surfactant composition, is water.
[0143] VI. Application
[0144] Generally speaking, the present invention is additionally
directed to a method of for killing or controlling weeds or
unwanted vegetation which comprises the steps of diluting a liquid
concentrate in a convenient amount of water to form a tank mix and
applying a herbicidally effective amount of the tank mix to the
foliage of the weeds or unwanted vegetation. Similarly included in
the invention is the method of killing or controlling weeds or
unwanted vegetation comprising the steps of diluting a solid
particulate concentrate in a convenient amount of water to form a
tank mix and applying a herbicidally effective amount of the tank
mix to the foliage of the weeds or unwanted vegetation.
[0145] The herbicidal composition of the present invention is
applied to plants at a rate sufficient to give the desired
biological effects: control of plant growth and early visual
symptoms of treatment. The amount of glyphosate and triclopyr, or
other pyridine analog, applied to plants in combination generally
provides a herbicidally-effective amount of the herbicides. The
amount of glyphosate and triclopyr, or other pyridine analogy,
applied to plants further is sufficient to provide early visual
symptoms of plant treatment without significantly reducing the
desired biological effect of the glyphosate. These application
rates are usually expressed as amount of glyphosate per unit area
treated, e.g. grams per hectare (g/ha). What constitutes a "desired
effect" varies according to the standards and practice of those who
investigate, develop, market and use compositions. Typically, the
amount of the composition applied per unit area to give 85% control
of a plant species as measured by growth reduction or mortality is
often used to define a commercially effective rate. Early visual
symptoms of treatment typically appear no later than about 4 days
after treatment, preferably no later than about 3 days after
treatment, more preferably no later than about 2 days after
treatment, and still more preferably no later than about 1 day
after treatment.
[0146] The selection of application rates that are herbicidally
effective for a composition of the invention is within the skill of
the ordinary agricultural scientist. Those of skill in the art will
likewise recognize that individual plant conditions, weather and
growing conditions, as well as the specific active ingredients and
their weight ratio in the composition, will influence the degree of
herbicidal effectiveness achieved in practicing this invention.
With respect to the use of glyphosate compositions, much
information is known about appropriate application rates. Over two
decades of glyphosate use and published studies relating to such
use have provided abundant information from which a weed control
practitioner can select glyphosate application rates that are
herbicidally effective on particular species at particular growth
stages in particular environmental conditions.
[0147] The herbicidal spray compositions included in the present
invention can be applied to the foliage of the plants to be treated
through any of the appropriate methods that are well known to those
having skill in the art. However, in one embodiment, the herbicidal
composition is applied using means other than a helicopter; stated
another way, in at least some embodiments the present invention is
directed to methods wherein the herbicidal composition is applied
using non-aerial means (i.e., ground application techniques. such
as a hand sprayer, rope-wick, etc.) or using a fixed-wing
aircraft.
[0148] Particularly important annual dicotyledonous plant species
for control of which a composition of the invention can be used are
exemplified without limitation by velvetleaf (Abutilon
theophrasti), pigweed (Amaranthus spp.), buttonweed (Borreria
spp.), oilseed rape, canola, indian mustard, etc. (Brassica spp.),
commelina (Commelina spp.), filaree (Erodium spp.), sunflower
(Helianthus spp.), morningglory (Ipomoea spp.), kochia (Kochia
scoparia), mallow (Malva spp.), wild buckwheat, smartweed, etc.
(Polygonum spp.), purslane (Portulaca spp.), russian thistle
(Salsola spp.), sida (Sida spp.), wild mustard (Sinapis arvensis)
and cocklebur (Xanthium spp.).
[0149] Particularly important annual monocotyledonous plant species
for control of which a composition of the invention can be used are
exemplified without limitation by wild oat (Avena fatua),
carpetgrass (Axonopus spp.), downy brome (Bromus tectorum),
crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crus-galli),
goosegrass (Eleusine indica), annual ryegrass (Lolium multiflorum),
rice (Oryza sativa), ottochloa (Ottochloa nodosa), bahiagrass
(Paspalum notatum), canarygrass (Phalaris spp.), foxtail (Setaria
spp.), wheat (Triticum aestivum) and corn (Zea mays).
[0150] Particularly important perennial dicotyledonous plant
species for control of which a composition of the invention can be
used are exemplified without limitation by mugwort (Artemisia
spp.), milkweed (Asclepias spp.), canada thistle (Cirsium arvense),
field bindweed (Convolvulus arvensis) and kudzu (Pueraria
spp.).
[0151] Particularly important perennial monocotyledonous plant
species for control of which a composition of the invention can be
used are exemplified without limitation by brachiaria (Brachiaria
spp.), bermudagrass (Cynodon dactylon), yellow nutsedge (Cyperus
esculentus), purple nutsedge (C. rotundus), quackgrass (Elymus
repens), lalang (Imperata cylindrica), perennial ryegrass (Lolium
perenne), guineagrass (Panicum maximum), dallisgrass (Paspalum
dilatatum), reed (Phragmites spp.), johnsongrass (Sorghum
halepense) and cattail (Typha spp.).
[0152] Other particularly important perennial plant species for
control of which a composition of the invention can be used are
exemplified without limitation by horsetail (Equisetum spp.),
bracken (Pteridium aquilinum), blackberry (Rubus spp.) and gorse
(Ulex europaeus).
[0153] If desired, the user can mix one or more adjuvants with a
composition of the invention and the water of dilution when
preparing the application composition. Such adjuvants can include
additional surfactant and/or an inorganic salt such as ammonium
sulfate with the aim of further enhancing herbicidal efficacy.
However, under most conditions a herbicidal method of use of the
present invention gives acceptable efficacy in the absence of such
adjuvants.
[0154] In a particular contemplated method of use of a composition
of the invention, the composition, following dilution in water, is
applied to foliage of crop plants genetically transformed or
selected to tolerate glyphosate, and simultaneously to foliage of
weeds or undesired plants growing in close proximity to such crop
plants. This method of use results in control of the weeds or
undesired plants while leaving the crop plants substantially
unharmed. Crop plants genetically transformed or selected to
tolerate glyphosate include those whose seeds are sold by Monsanto
Company or under license from Monsanto Company bearing the Roundup
Ready.RTM. trademark. These include, without restriction, varieties
of cotton, soybean, canola, sugar beet, wheat and corn.
[0155] Plant treatment compositions can be prepared simply by
diluting a concentrate composition of the invention in water.
Application of plant treatment compositions to foliage is
preferably accomplished by spraying, using any conventional means
for spraying liquids, such as spray nozzles, atomizers or the like.
Compositions of the invention can be used in precision farming
techniques, in which apparatus is employed to vary the amount of
pesticide applied to different parts of a field, depending on
variables such as the particular plant species present, soil
composition, etc. In one embodiment of such techniques, a global
positioning system operated with the spraying apparatus can be used
to apply the desired amount of the composition to different parts
of a field.
[0156] VII. Definitions
[0157] The terms "hydrocarbon" and "hydrocarbyl" as used herein
describe organic compounds or radicals consisting exclusively of
the elements carbon and hydrogen. These moieties include alkyl,
alkenyl, alkynyl, and aryl moieties. These moieties also include
alkyl, alkenyl, alkynyl, and aryl moieties substituted with other
aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl
and alkynaryl. Unless otherwise indicated, these moieties
preferably comprise 1 to 30 carbon atoms.
[0158] The term "hydrocarbylene" as used herein describes radicals
joined at two ends thereof to other radicals in an organic
compound, and which consist exclusively of the elements carbon and
hydrogen. These moieties include alkylene, alkenylene, alkynylene,
and arylene moieties. These moieties also include alkyl, alkenyl,
alkynyl, and aryl moieties substituted with other aliphatic or
cyclic hydrocarbon groups, such as alkaryl, alkenaryl and
alkynaryl. Unless otherwise indicated, these moieties preferably
comprise 1 to 30 carbon atoms.
[0159] The "substituted hydrocarbyl" moieties described herein are
hydrocarbyl moieties which are substituted with at least one atom
other than carbon, including moieties in which a carbon chain atom
is substituted with a hetero atom such as nitrogen, oxygen,
silicon, phosphorous, boron, sulfur, or a halogen atom. These
substituents include halogen, heterocyclo, alkoxy, alkenoxy,
alkynoxy, aryloxy, hydroxy, protected hydroxy, ketal, acyl,
acyloxy, nitro, amino, amido, cyano, thiol, acetal, sulfoxide,
ester, thioester, ether, thioether, hydroxyalkyl, urea, guanidine,
amidine, phosphate, amine oxide, and quaternary ammonium salt.
[0160] The "substituted hydrocarbylene" moieties described herein
are hydrocarbylene moieties which are substituted with at least one
atom other than carbon, including moieties in which a carbon chain
atom is substituted with a hetero atom such as nitrogen, oxygen,
silicon, phosphorous, boron, sulfur, or a halogen atom. These
substituents include halogen, heterocyclo, alkoxy, alkenoxy,
alkynoxy, aryloxy, hydroxy, protected hydroxy, ketal, acyl,
acyloxy, nitro, amino, amido, cyano, thiol, acetal, sulfoxide,
ester, thioester, ether, thioether, hydroxyalkyl, urea, guanidine,
amidine, phosphate, amine oxide, and quaternary ammonium salt.
[0161] Unless otherwise indicated, the alkyl groups described
herein are preferably lower alkyl containing from one to 18 carbon
atoms in the principal chain and up to 30 carbon atoms. They may be
straight or branched chain or cyclic and include methyl, ethyl,
propyl, isopropyl, n-butyl, isobutyl, hexyl, 2-ethylhexyl, and the
like.
[0162] Unless otherwise indicated, the alkenyl groups described
herein are preferably lower alkenyl containing from two to 18
carbon atoms in the principal chain and up to 30 carbon atoms. They
may be straight or branched chain or cyclic and include ethenyl,
propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and the
like.
[0163] Unless otherwise indicated, the alkynyl groups described
herein are preferably lower alkynyl containing from two to 18
carbon atoms in the principal chain and up to 30 carbon atoms. They
may be straight or branched chain and include ethynyl, propynyl,
butynyl, isobutynyl, hexynyl, and the like.
[0164] The terms "aryl" as used herein alone or as part of another
group denote optionally substituted homocyclic aromatic groups,
preferably monocyclic or bicyclic groups containing from 6 to 12
carbons in the ring portion, such as phenyl, biphenyl, naphthyl,
substituted phenyl, substituted biphenyl or substituted naphthyl.
Phenyl and substituted phenyl are the more preferred aryl.
[0165] The term "aralkyl" as used herein denotes a group containing
both alkyl and aryl structures such as benzyl.
[0166] As used herein, the alkyl, alkenyl, alkynyl, aryl and
aralkyl groups can be substituted with at least one atom other than
carbon, including moieties in which a carbon chain atom is
substituted with a hetero atom such as nitrogen, oxygen, silicon,
phosphorous, boron, sulfur, or a halogen atom. These substituents
include hydroxy, nitro, amino, amido, nitro, cyano, sulfoxide,
thiol, thioester, thioether, ester and ether, or any other
substituent which can increase the compatibility of the surfactant
and/or its efficacy enhancement in the glyphosate formulation
without adversely affecting the storage stability of the
formulation.
[0167] The terms "halogen" or "halo" as used herein alone or as
part of another group refer to chlorine, bromine, fluorine, and
iodine. Fluorine substituents are often preferred in surfactant
compounds.
[0168] Unless otherwise indicated, the term "hydroxyalkyl" includes
alkyl groups substituted with at least one hydroxy group, and
includes bis(hydroxyalkyl)alkyl, tris(hydroxyalkyl)alkyl and
poly(hydroxyalkyl)alkyl groups. Preferred hydroxyalkyl groups
include hydroxymethyl (--CH.sub.2OH), and hydroxyethyl
(--C.sub.2H.sub.4OH), bis(hydroxymethyl)methyl
(--CH(CH.sub.2OH).sub.2), and tris(hydroxymethyl)methyl
(--C(CH.sub.2OH).sub.3).
[0169] The term "cyclic" as used herein alone or as part of another
group denotes a group having at least one closed ring, and includes
alicyclic, aromatic (arene) and heterocyclic groups.
[0170] The terms "heterocyclo" or "heterocyclic" as used herein
alone or as part of another group denote optionally substituted,
fully saturated or unsaturated, monocyclic or bicyclic, aromatic or
nonaromatic groups having at least one heteroatom in at least one
ring, and preferably 5 or 6 atoms in each ring. The heterocyclo
group preferably has 1 or 2 oxygen atoms, 1 or 2 sulfur atoms,
and/or 1 to 4 nitrogen atoms in the ring, and may be bonded to the
remainder of the molecule through a carbon or heteroatom. Exemplary
heterocyclo include heteroaromatics such as furyl, thienyl,
pyridyl, oxazolyl, pyrrolyl, indolyl, quinolinyl, or isoquinolinyl
and the like, and non-aromatic heterocyclics such as
tetrahydrofuryl, tetrahydrothienyl, piperidinyl, pyrrolidino, etc.
Exemplary substituents include one or more of the following groups:
hydrocarbyl, substituted hydrocarbyl, keto, hydroxy, protected
hydroxy, acyl, acyloxy, alkoxy, alkenoxy, alkynoxy, aryloxy,
halogen, amido, amino, nitro, cyano, thiol, thioester, thioether,
ketal, acetal, ester and ether.
[0171] The term "heteroaromatic" as used herein alone or as part of
another group denote optionally substituted aromatic groups having
at least one heteroatom in at least one ring, and preferably 5 or 6
atoms in each ring. The heteroaromatic group preferably has 1 or 2
oxygen atoms, 1 or 2 sulfur atoms, and/or 1 to 4 nitrogen atoms in
the ring, and may be bonded to the remainder of the molecule
through a carbon or heteroatom. Exemplary heteroaromatics include
furyl, thienyl, pyridyl, oxazolyl, pyrrolyl, indolyl, quinolinyl,
or isoquinolinyl and the like. Exemplary substituents include one
or more of the following groups: hydrocarbyl, substituted
hydrocarbyl, keto, hydroxy, protected hydroxy, acyl, acyloxy,
alkoxy, alkenoxy, alkynoxy, aryloxy, halogen, amido, amino, nitro,
cyano, thiol, thioether, thioester, ketal, acetal, ester and
ether.
[0172] The term "acyl," as used herein alone or as part of another
group, denotes the moiety formed by removal of the hydroxyl group
from the group --COOH of an organic carboxylic acid, e.g., RC(O)--,
wherein R is R.sup.1, R.sup.1O--, R.sup.1R.sup.2N--, or R.sup.1S--,
R.sup.1 is hydrocarbyl, heterosubstituted hydrocarbyl, or
heterocyclo and R.sup.2 is hydrogen, hydrocarbyl or substituted
hydrocarbyl.
[0173] The term "acyloxy," as used herein alone or as part of
another group, denotes an acyl group as described above bonded
through an oxygen linkage (--O--), e.g., RC(O)O-- wherein R is as
defined in connection with the term "acyl."
[0174] The term "pesticide" includes chemicals and microbial agents
used as active ingredients of products for control of crop and lawn
pests and diseases, animal ectoparasites, and other pests in public
health. The term also includes plant growth regulators, pest
repellants, synergists, herbicide safeners (which reduce the
phytotoxicity of herbicides to crop plants) and preservatives, the
delivery of which to the target may expose dermal and especially
ocular tissue to the pesticide. Such exposure can arise by drift of
the pesticide from the delivery means to the person performing the
application of the pesticide or being present in the vicinity of an
application.
[0175] When a maximum or minimum "average number" is recited herein
with reference to a structural feature such as oxyethylene units or
glucoside units, it will be understood by those skilled in the art
that the integer number of such units in individual molecules in a
surfactant preparation typically varies over a range that can
include integer numbers greater than the maximum or smaller than
the minimum "average number". The presence in a composition of
individual surfactant molecules having an integer number of such
units outside the stated range in "average number" does not remove
the composition from the scope of the present invention, so long as
the "average number" is within the stated range and other
requirements are met.
[0176] Herbicidal effectiveness is one of the biological effects
that can be enhanced through this invention. "Herbicidal
effectiveness," as used herein, refers to any observable measure of
control of plant growth, which can include one or more of the
actions of (1) killing, (2) inhibiting growth, reproduction or
proliferation, and (3) removing, destroying, or otherwise
diminishing the occurrence and activity of plants. The herbicidal
effectiveness data set forth herein report "control" as a
percentage following a standard procedure in the art which reflects
a visual assessment of plant mortality and growth reduction by
comparison with untreated plants, made by technicians specially
trained to make and record such observations. In all cases, a
single technician makes all assessments of percent control within
any one experiment or trial. Such measurements are relied upon and
regularly reported by Monsanto Company in the course of its
herbicide business.
EXAMPLES
[0177] The following Examples are provided for illustrative
purposes only and are not intended to limit the scope of the
present invention. The Examples will permit better understanding of
the invention and perception of its advantages and certain
variations of execution.
[0178] Section 1. Formulations
[0179] Aqueous herbicide formulations were generated from
commercially available glyphosate isopropylamine, triclopyr
triethylamine and various surfactants in the ratios indicated in
Tables 1.1 and 1.2.
6TABLE 1.1 Formulations: Glyphosate Triclopyr Sur- (G); (T); G:T
fac- Surf G:surf CODE g ae/L.sup.a g ae/L.sup.a w:w.sup.b tant w/v
%.sup.c w:w.sup.d RUP1 351 ae (30.6%) FS1 11.9 3.0 RUP2 443 ae
(37.2%) FS1 9.81 4.5 RU1 27% Roundup FS4 4.11 3.5 FG1 46.3% ae F2M
142 7.71 18.5:1 FS1 4.11 3.5 F1M 142 3.85 18.5:0.5 FS1 4.11 3.5 F1C
142 3.85 18.5:0.5 FS4 5.4 3.6 F2C 142 7.66 18.5:1 FS4 5.3 3.6 F3M
143 15.4 18.6:2 FS1 4.11 3.5 F5M 7.38 0.72 20.5:2 FS1 0.21 3.6 F4C
151.3 24.48 18.5:3 FS4 5.7 3.6 F11M 7.38 0.36 20.5:1 FS1 0.21 3.6
F8M 142 92.5 18.5:12 FS1 4.11 3.5 F9M 142 61.7 18.5:8 FS1 4.11 3.5
F10M 142 40.9 18.5:5.3 FS1 4.11 3.5 .sup.aGlyphosate and triclopyr
are expressed as the acid equivalent load (g ae/L). The densities
of the concentrate formulations are in the range 1.06 to 1.17 g/ml.
The ready-to-use formulation has a density of approx. 1.004 g/ml.
.sup.bThe glyphosate/triclopyr w/w ratio given in terms of the acid
equivalent weights. .sup.cThe surfactant load is expressed as the
weight/volume %, i.e. g/100 ml. .sup.dThe glyphosate/surfactant w/w
ratio, i.e., g ae/g surfactant per kg of formulation.
[0180]
7TABLE 1.2 Formulations. Glyphosate Triclopyr (T); (G); g/Kg g/Kg;
G:T CODE (62% ai).sup.a (44% ai).sup.b w:w.sup.c Surfactant w/w;
%.sup.d F14X 290.3 25.5 18:1.13 FS3 5 F13X 290.3 51 18:2.25 FS3 5
F12X 290.3 101 18:4.50 FS3 5 F6X 290.4 60 18:2.66 FS3 5 F4X 290.4
67.6 18:3 FS3 5 F3X 290.3 45 18:2 FS3 5 F2X 290.3 22.5 18:1 FS3 5
F1X 290.3 11.3 18:0.5 FS3 5 F0X 290.3 0 18:0 FS3 5 F14M 290.3 25.5
18:1.13 FS1 5 F13M 290.3 51 18:2.25 FS1 5 F12M 290.3 101 18:4.50
FS1 5 F6M 290.4 60 18:2.66 FS1 5 F4M 290.4 67.6 18:3 FS1 5 F5M 16.1
2.3 1:0.1 FS1 5 F3M 290.3 45 18:2 FS1 5 F2M 290.3 22.5 18:1 FS1 5
F1M 290.3 11.3 18:0.5 FS1 5 F0M 290.3 0 18:0 FS1 5 F15C 290.3 152.2
18:6.76 FS4 5 F14C 290.3 25.5 18:1.13 FS4 5 F13C 290.3 51 18:2.25
FS4 5 F12C 290.3 101 18:4.50 FS4 5 F4C 290.3 67.6 18:3 FS4 5 F3C
290.3 45 18:2 FS4 5 F2C 290.3 22.5 18:1 FS4 5 F1C 290.3 11.3 18:0.5
FS4 5 F0C 290.3 0 18:0 FS4 5 F6Y 290.3 59.9 18:2.66 FS5 3.5 F3Y
290.3 45 18.2 FS5 3.5 F4Y 290.3 67.6 18:3 FS5 3.5 F7Y 290.3 90.1
18:4 FS5 3.5 .sup.aGlyphosate load expressed as the weight of a
standard (62% ai glyphosate) used per 1000 g. The densities of the
concentrate formulations are in the range 1.06 to 1.17 g/ml. The
ready-to-use formulation has a density of approx. 1.004 g/ml.
.sup.bTriclopyr load expressed as the weight of a standard (44.3%
ai triclopyr) used per 1000 g. The densities of the concentrate
formulations are in the range 1.06 to 1.17 g/ml. The ready-to-use
formulation has a density of approx. 1.004 g/ml. .sup.cThe
glyphosate/triclopyr w/w ratio is given in terms of the % ai/% ai.
.sup.dThe surfactant is expressed as the w/w % i.e., weight of
surfactant standard per 100 g. KEY TO SURFACTANTS: 1. FS1
surfactant composition is a mixture of tallowamines and phosphate
esters, as described in U.S. Pat. No. 5,703,015. 2. FS2 surfactant
composition is a mixture of tallowamines and phosphate esters, as
described in U.S. Pat. No. 5,703,015. 3. FS3 surfactant composition
is a mixture of a tallowamine ethoxylate with other surfactants. 4.
FS4 is a Cocoamine 5EO. 5. FS5 is a Cocoamine 5EO.
[0181] Section 2. Stability Test & Results:
Example 2.1
Stability Test
[0182] Materials & Methods:
[0183] Various formulations were maintained at constant temperature
for a fixed period and monitored for changes in color, homogeneity
and appearance after thawing. The formulations were also cycled
through temperature extremes i.e., at low temperatures of
-20.degree. C. and -5.degree. C. for the fixed period then raised
to the higher temperatures of 20.degree. C. and 5.degree. C.
respectively and changes monitored. Results for a 4-week study are
tabulated below.
[0184] Results:
8TABLE 2.1A Stability Results. Temperature Stability Results (4
weeks) Appearance after Formulation % wt ai % wt ai Surfactant
-20/+20.degree. C. -5/+5.degree. C. thawing CODE Glyphosphate
Triclopyr (5%) RT (-19.9.degree. C.) (-6.7.degree. C.) 4.5.degree.
C. 60.degree. C. -10.degree. C. to Room Temp. F12X 18 4.50 FS3 No
Color at No No No Solid, No crystals, change bottom change change
change crystals homogenous after mixing F13X 18 2.25 FS3 No Color
at No No No Solid, No crystals, change bottom change change change
crystals homogenous after mixing F14X 18 1.13 FS3 No Color at No No
No Solid, No crystals, change bottom change change change crystals
homogenous after mixing F0X 18 0.00 FS3 No Color at No No No Solid,
No crystals, change bottom change change change crystals homogenous
after mixing F12M 18 4.50 FS1 No X'tals No No No Solid, Crystals
remain change 10% change change change crystals on bottom (10%)
(btm) F13M 18 2.25 FS1 No Color at No No No Solid, No crystals,
change bottom change change change crystals homogenous after mixing
F14M 18 1.13 FS1 No Color at No No No Solid, No crystals, change
bottom change change change crystals homogenous after mixing F0M 18
0.00 FS1 No Color at No No No Solid, No crystals, change bottom
change change change crystals homogenous after mixing F15C 18 6.76
FS4 No Color at No No No Solid, No crystals, change bottom change
change change crystals homogenous after mixing F12C 18 4.50 FS4 No
Color at No No No Solid, No crystals, change bottom change change
change crystals homogenous after mixing F13C 18 2.25 FS4 No Color
at No No No Solid, No crystals, change bottom change change change
crystals homogenous after mixing F14C 18 1.13 FS4 No Color at No No
No Solid, No crystals, change bottom change change change crystals
homogenous after mixing F0M 18 0.00 FS3 No Color at No No No Solid,
No crystals, change bottom change change change crystals homogenous
after mixing
[0185]
9TABLE 2.1B Stability Results. % wt ai Surfac- -20/ CODE Triclopyr
tant +20.degree. C. 60.degree. C. F6X 2.66 FS3 crystals All
formulations No layered from freeze layering thaw F3X 2 FS3 clear
All formulations No layered from freeze layering thaw F4X 3 FS3
crystals All formulations No layered from freeze layering thaw F6M
2.66 FS1 crystals All formulations No layered from freeze layering
thaw F3M 2 FS1 clear All formulations No layered from freeze
layering thaw F4M 3 FS1 crystals All formulations No layered from
freeze layering thaw F6Y 2.66 FS5 clear All formulations No layered
from freeze layering thaw F3Y 2 FS5 clear All formulations No
layered from freeze layering thaw F4Y 3 FS5 clear All formulations
No layered from freeze layering thaw F7Z 4 FS5 + crystals All
formulations No NMP layered from freeze layering thaw
[0186] Section 3. Greenhouse Test & Results.
[0187] Objective: Greenhouse study of potential Roundup Brushkiller
formulations on Red Maple and Red Oak.
[0188] Materials & Methods: Standard post emerge herbicide
application procedures were used, such the procedure described
below. The herbicide formulations tested are listed in Table 3.1
below. Additional information is available in Tables 1.1 and
1.2.
[0189] Seeds of the plant species indicated were planted in 3.5 in
square pots in a soil mix which was previously steam sterilized and
prefertilized with a 14-14-14 NPK slow release fertilizer at a rate
of 100 g/ft.sup.3. The pots were placed in a greenhouse with
sub-irrigation. About one week after emergence, seedlings were
thinned as needed, including removal of any unhealthy or abnormal
plants, to create a uniform series of test pots.
[0190] The plants were maintained for the duration of the test in
the greenhouse where they received a minimum of 14 hours of light
per day. If natural light was insufficient to achieve the daily
requirement, artificial light with an intensity of approximately
475 microeinsteins was used to make up the difference. Exposure
temperatures were not precisely controlled but averaged about
27.degree. C. during the day and about 21.degree. C. during the
night. Plants were sub-irrigated throughout the test to ensure
adequate soil moisture levels.
[0191] Pots were assigned to different treatments in a randomized
experimental design with 6 replications. A set of pots was left
untreated as a reference against which effects of the treatments
could later be evaluated.
[0192] Application of glyphosate compositions was made by spraying
with a track sprayer fitted with a flateven 8008E nozzle calibrated
to deliver a spray volume of 1348 liters per hectare (l/ha) at a
pressure of 165 kilopascals (kPa). After treatment, pots were
returned to the greenhouse until ready for evaluation. Treatments
were made using dilute aqueous compositions.
[0193] For evaluation of herbicidal effectiveness, all plants in
the test were examined by a single practiced technician, who
recorded percent control, a visual measurement of the effectiveness
of each treatment by comparison with untreated plants. Control of
0% indicates no effect, and control of 100% indicates that all of
the plants are completely dead. Control of 85% or more is in most
cases considered acceptable for normal herbicide use; however in
greenhouse tests such as those for the examples it is normal to
apply compositions at rates which give less than 85% control, as
this makes it easier to discriminate among compositions having
different levels of effectiveness. The reported % control values
represent the average for all replicates of each treatment.
10TABLE 3.1 Glyphosate Formulations for Greenhouse Testing: w/w %
w/w % Amt Other Formulation Glyph. Glyph. Amt., g Salt surfact.
active; Triclopyr Code ae ai ae/L Form Surfact. w/w % Triclopyr amt
% ai F3X 13.34 18.00 143.70 IPA FS3 5.0% Hammer 2.0% F2X 13.34
18.00 143.27 IPA FS3 5.0% Hammer 1.0% F1X 13.34 18.00 143.07 IPA
FS3 5.0% Hammer 0.5% F0X 13.34 18.00 142.78 IPA FS3 5.0% F3M 13.34
18.00 143.60 IPA FS1 5.0% Hammer 2.0% F2M 13.34 18.00 143.18 IPA
FS1 5.0% Hammer 1.0% F1M 13.34 18.00 142.96 IPA FS1 5.0% Hammer
0.5% F0M 13.34 18.00 142.75 IPA FS1 5.0% F4C 13.34 18.00 143.69 IPA
FS4 5.0% Hammer 3.0% F3C 13.34 18.00 143.26 IPA FS4 5.0% Hammer
2.0% F2C 13.34 18.00 142.84 IPA FS4 5.0% Hammer 1.0% F1C 13.34
18.00 142.63 IPA FS4 5.0% Hammer 0.5% F0C 13.34 18.00 142.83 IPA
FS4 5.0%
[0194]
11 COMMERCIAL PRODUCTS ACTIVE % Ai RUP BSK CONC GLYPH 27.0 BBG
TRICL 8.0 ENF BSK CONC TRICL 8.8
[0195] Results:
12TABLE 3.2A GREENHOUSE STUDY OF POTENTIAL ROUNDUP BRUSHKILLER
FORMULATIONS ON RED MAPLE AND RED OAK % CTRL 5 DAT % CTRL 5 DAT
CHEMICAL FORM MIX RATE MAPLE MAPLE MAPLE MAPLE OAK OAK OAK TRT
FORMULN DESIG 0Z/GAL REP 1 REP 2 REP 3 AVE. REP 1 REP 2 AVE. 1 F3X
SL 6 55.0 30.0 65.0 50.0 0.0 30.0 15.0 2 F2X SL 6 30.0 20.0 40.0
30.0 0.0 40.0 20.0 3 F1X SL 6 20.0 50.0 20.0 30.0 45.0 70.0 57.5 4
F0X SL 6 5.0 5.0 10.0 6.7 5.0 5.0 5.0 5 F3M SL 6 55.0 70.0 70.0
65.0 45.0 10.0 27.5 6 F2M SL 6 25.0 35.0 70.0 43.3 10.0 10.0 10.0 7
F1M SL 6 30.0 50.0 25.0 35.0 5.0 30.0 17.5 8 F0M SL 6 40.0 35.0
30.0 35.0 5.0 20.0 12.5 9 F4C SL 6 55.0 55.0 65.0 58.3 80.0 10.0
45.0 10 F3C SL 6 55.0 55.0 40.0 50.0 5.0 20.0 12.5 11 F2C SL 6 40.0
50.0 35.0 41.7 75.0 5.0 40.0 12 F1C SL 6 35.0 35.0 20.0 30.0 5.0
10.0 7.5 13 F0C SL 6 15.0 5.0 10.0 10.0 0.0 5.0 2.5 14 RUP BSK SL 6
30.0 25.0 30.0 28.3 0.0 70.0 35.0 CONC 15 ORTHO SL 4 60.0 75.0 20.0
51.7 45.0 50.0 47.5 BBG 16 ENF BSK SL 4 25.0 25.0 30.0 26.7 10.0
5.0 7.5 CONC 17 UNTREATED 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CONTROL
[0196]
13TABLE 3.2B GREENHOUSE STUDY OF POTENTIAL ROUNDUP BRUSHKILLER
FORMULATIONS ON RED MAPLE AND RED OAK % CTRL 21 DAT % CTRL 21 DAT
CHEMICAL FORM MIX RATE MAPLE MAPLE MAPLE MAPLE OAK OAK OAK TRT
FORMULN DESIG 0Z/GAL REP 1 REP 2 REP 3 AVE. REP 1 REP 2 AVE. 1 F3X
SL 6 100.0 100.0 100.0 100.0 95.0 100.0 97.5 2 F2X SL 6 100.0 100.0
100.0 100.0 100.0 100.0 100.0 3 F1X SL 6 100.0 100.0 100.0 100.0
100.0 100.0 100.0 4 F0X SL 6 100.0 100.0 100.00 100.0 80.0 100.0
90.0 5 F3M SL 6 100.0 100.0 100.0 100.0 80.0.0 100.0 90.0 6 F2M SL
6 100.0 100.0 100.0 100.0 95.0 95.0 95.0 7 F1M SL 6 100.0 100.0
100.0 100.0 99.0 99.0 99.0 8 F0M SL 6 100.0 100.0 100.0 100.0 75.0
88.0 81.5 9 F4C SL 6 100.0 100.0 100.00 100.0 88.0 100.0 94.0 10
F3C SL 6 100.0 100.00 100.0.0 100.0 90.0 100.0 95.0 11 F2C SL 6
100.0 100.00 100.0 100.0 100.0 98.0 99.0 12 F1C SL 6 100.0 100.0
100.0 100.0 99.0 99.0 99.0 13 F0C SL 6 100.0 95.0 88.0 94.3 45.0
100.0 72.5 14 RUP BSK SL 6 100.0 100.0 100.0 100.0 100.0 95.0 97.5
CONC 15 ORTHO BBG SL 4 100.0 100.0 100.0 100.0 100.0.0 100.0 100.0
16 ENF BSK SL 4 100.0 100.0 100.0 100.0 100.0 100.0 100.0 CONC 17
UNTREATED 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CONTROL
[0197] Discussion:
[0198] 5 DAT: The maples exhibited more injury as the triclopyr
level went up. The oaks responded more inconsistently than the
maples in this regard. Formulation F1X provided the best control of
oak at this rating. Only formulations F3M and F4C provided more
injury than Ortho Brush-B-Gone (BBG) on maple. The surfactant FS4
proved to be slightly better overall than did the tallowamine
formulation FS1. The other tallowamine FS3 was consistently weaker
than both other surfactants.
[0199] The current Roundup 27% brushkiller formulation failed to
provide the same level of injury as that of the Brush-B-Gone
product. It did, however, outperform Enforcer (ENF) on both
species.
[0200] 21 DAT: The maples proved to be much easier to control than
the oaks at this evaluation time. Only F0C (no triclopyr) failed to
provide 100% control. The oak control went up as the triclopyr
level decreased. The lowest level of triclopyr was the best on oak
and all triclopyr-containing formulations appeared to perform
better than glyphosate alone. Tallowamine formulation FS3 seemed to
be the best surfactant on oak.
[0201] Sections 4/5. Field Test & Results.
Example 4.1
[0202] Objective: Demonstrate that F3M and F5M formulations provide
commercially acceptable weed control.
[0203] Materials and Methods: A Ready-To-Use F5M and concentrate
F3M brush killer formulations were evaluated. F5M RTU is
constructed as 1% glyphosate, isopropylamine salt and 0.10%
triclopyr, triethylamine salt, while F3M concentration formulation
is constructed as 18% a.i. glyphosate and 2% a.i. triclopyr.
[0204] Nine field trials were conducted at various geographic
regions in the U.S. to evaluate poison ivy, poison oak, kudzu, and
multiflora rose control when treated with F5M and F3M.
14TABLE 4.1.1 Location and Number of Brush Tests by Species.
Primary Species Tested Poison Poison Multiflora Geographic Ivy Oak
Rose Kudzu Region State Number of tests Mid-West Illinois 1 1 Ohio
1 Central Missouri 1 South Alabama 1 1 Mississippi 1 1 West
California 1
[0205] The brush tests were conducted on preexisting brush
infestations typically located along and within fence and tree
lines during June through August. All brush species were
well-established and exhibiting complete foliation of leaf tissue
at the time of treatment.
[0206] Each test was established using a randomized complete block
design (RCBD) with each of the formulations being applied to 3, 15
ft.sup.2 plots. Equal volumes of formulation were applied to each
plot either with a RTU Pull n' Spray.RTM. sprayer used to apply,
the RTU F5M formulation a Roundup.RTM. Herbicide Sprayer to apply
the concentrate F3M formulation. F5M was applied based on 1 gal of
solution treats 300 sq ft (equivalent to 145 gallons per acre) and
the standard application volume for a spray to wet treatment. F3M
concentrate formulation was applied at a rate of 6 oz/gallon spray
to wet.
[0207] Brush control ratings were evaluated at 1, 3, 21 and 90 days
after treatment (DAT). Visual assessment of formulation efficacy
was assessed on a 0 to 100% scale based on brush control (chorosis,
necrosis and kill) compared to the untreated plots. Values close to
0% indicate no visual presence of brush damage by a formulation,
while values approaching 100% indicate complete kill of a brush
species compared to untreated plots. In addition, values greater
than 80% control indicate that a product is supplying the industry
standard commercially acceptable weed/brush control.
[0208] To quantify differences in percent brush control among
formulations for each weed species by observation date, Duncan's
multiple range test was applied and evaluated at P=0.05.
[0209] Results:
15TABLE 4.1.2 F3M and F5M gave commercial control up to 90 DAT on
Poison Ivy and Poison Oak. Poison Ivy Poison Oak DAT 1 3 7 21 90 1
3 7 21 90 Trt. Formuln. % Control 1 F3M 6a 36a 94b 100a 100a 0a 10b
85a 100a 100a 2 F5M 7a 36a 96a 100a 100a 0a 23a 80b 100a 100a 3
Untreated 0b 0b 0c 0b 0b 0a 0c 0c 0b 0b Check Means followed by
same letter, for each weed species, do not significantly differ (P
= 0.05, Duncan's multiple range test)
[0210]
16TABLE 4.1.3 F3M and F5M gave commercial control up to 90 DAT on
Multiflora Rose and Kudzu. Multiflora Rose Kudzu DAT 1 3 7 21 90 1
3 7 21 90 Trt. Formuln. % Control 1 F3M 6a 34a 78a 93a 100a 11a 42b
70b 90a 88a 2 F5M 6a 46b 80a 94a 100a 10a 45a 85a 93a 90a 3
Untreated 0b 0c 0b 0b 0b 0b 0c 0c 0b 0b Check Means followed by
same letter, for each weed species, do not significantly differ (P
= 0.05, Duncan's multiple range test)
[0211]
17TABLE 4.1.4 F3M and F5M gave commercial control up to 90 DAT on
all brush tests combined. Overall Brush.sup.1 DAT 1 3 7 21 90 Trt.
Formuln. % Control 1 F3M 6a 34b 86a 96a 98a 2 F5M 7a 39a 90a 97a
98a 3 Untreated 0b 0c 0b 0b 0b Chk .sup.1Four brush species were
tested poison oak, poison ivy, multiflora rose, and kudzu across 9
brush tests Means followed by same letter, for each weed species,
do not significantly differ (P = 0.05, Duncan's multiple range
test)
[0212] Discussion:
[0213] F5M and F3M provided commercial control of tough to control
brush. At 90 DAT brush control for all species tested ranged
between 90 and 100% control (Tables 4.2.1 through 4.3.4). F5M and
F3M tested at various regions and brush species will deliver
effective weed control of unwanted vegetation up to 90DAT.
Example 4.2
Evaluation on Poison Ivy
[0214] Objectives: Evaluate various formulations on Poison Ivy.
[0215] Materials & Methods: Formulations tabulated below were
field tested for 14 days in September to October at Clemson, S.C.
See Tables 1.1 and 1.2 for description of product formulations.
18TABLE 4.2.1 Results: Rate % injury 14 DAT Product Form. in
oz/1gallon Poison ivy 1. BSK 6 oz 80 2. F1M 6 oz 80 3. F2M 6 oz
91.6 4. F4C 6 oz 100 5. F3M 6 oz 100 6. BBG 4 oz 70 7. BBG + FS1 4
oz + 3 oz 86.4 8. Untreated 0 10* Check *Untreated Check displayed
some natural yellowing due to senescence, or aging.
Example 4.3
Evaluation on Kudzu
[0216] Materials & Methods: Field evaluations of experimental
formulations tabulated below were conducted on brush species (Kudzu
Roadside) in Mississippi.
19TABLE 4.3.1 Formulation % ai Triclopyr Code % ai Gly IPA TEA
Surfactant % Surfactant F2M 18 1 FS1 5 F1M 18 0.5 FS1 5 F1C 18 0.5
FS4 5 F2C 18 1 FS4 5 F3M 18 2 FS1 5 F4C 18 3 FS4 5 BSK or RU1 27 0
FS1 ? BBG 0 0
[0217]
20TABLE 4.3.2 Results: Form Rate fl Trt # Code oz/gal 7DAT**
10DAT** 30DAT** 1 BSK 6 41.7 83.3 100 2 F1M 6 36.7 80 100 3 F2M 6
45 87 100 4 F4C 6 46.7 78.3 100 5 F3M 6 36.7 73.3 98.3 6 BBG 4 33.3
23.3 73.3 7 BBG + FS1 43 40 30 85 8 Untreated 0 0 0 Check
**Tabulated values are the mean of 3 tests.
Example 4.4
Field Test at Mississippi #2
[0218] Materials & Methods: Evaluations on experimental
formulations were conducted on brush species at various locations
and summarized below (St Louis, Clemson S.C., Mississippi).
21TABLE 4.4.1 Results: Summary of Brush Tests Date First Formln DAT
Location Rated Code Formln 5 7 10 14 16 30 42 Weed St Louis July
F3M 18 + 2 90 100 100 Poison Ivy St Louis July F2M 18 + 1 80 100
100 Poison Ivy St Louis July F1M 18 + 0.5 70 100 100 Poison Ivy St
Louis July F4C 18 + 3 95 100 100 Poison Ivy St Louis July RU1 27%
R'up 50 95 100 Poison Ivy Brush St Louis July BBG Brush-B-Gone 85
100 100 Poison Ivy St Louis July ENF Enforcer 85 100 100 Poison Ivy
St Louis July F3M 18 + 2 85 100 100 Fesc/Blue St Louis July F2M 18
+ 1 80 100 100 Fesc/Blue St Louis July F1M 18 + 0.5 85 100 100
Fesc/Blue St Louis July F4C 18 + 3 90 100 100 Fesc/Blue St Louis
July RU1 27% R'up 50 95 100 Fesc/Blue Brush St Louis July BBG
Brush-B-Gon 50 65 70 Fesc/Blue St Louis July ENF Enforcer 20 15 0
Fesc/Blue St Louis July F3M 18 + 2 80 98 100 Golden Rod St Louis
July F2M 18 + 1 65 88 98 Golden Rod St Louis July F1M 18 + 0.5 35
85 100 Golden Rod St Louis July F4C 18 + 3 90 98 98 Golden Rod St
Louis July RU1 27% R'up 50 95 95 Golden Rod Brush St Louis July BBG
Brush-B-Gon 40 65 65 Golden Rod St Louis July ENF Enforcer 30 75 75
Golden Rod St Louis July F3M 18 + 2 80 100 100 Fesc/Blue St Louis
July F2M 18 + 1 70 100 100 Fesc/Blue St Louis July F1M 18 + 0.5 50
100 100 Fesc/Blue St Louis July F4C 18 + 3 70 100 100 Fesc/Blue St
Louis July RU1 27% R'up 85 98 98 Fesc/Blue Brush St Louis July BG
Brush-B-Gon 0 0 0 Fesc/Blue St Louis July ENF Enforcer 0 0 0
Fesc/Blue Miss October F3M 18 + 2 37 73 98 Kudzu Miss October F2M
18 + 1 45 87 100 Kudzu Miss October F1M 18 + 0.5 37 80 100 Kudzu
Miss October F4C 18 + 3 47 78 100 Kudzu Miss October RU1 27% R'up
42 83 100 Kudzu Brush Miss October BBG Brush-B-Gon 33 23 73 Kudzu
Miss October BBG + FS1 Brush-B-Gon+ 40 30 85 Kudzu Clem October RU1
27% R'up 80 Poison Ivy Brush Clem October F1M 18 + 0.5 80 Poison
Ivy Clem October F2M 18 + 1 91.6 Poison Ivy Clem October F4C 18 + 3
100 Poison Ivy Clem October BBG Brush-B-Gon 70 Poison Ivy Clem
October BBG + FS1 Brush-B-Gon+ 86.4 Poison Ivy Clem October F3M 18
+ 2 100 Poison Ivy
[0219]
22TABLE 4.4.2 Grand Brush Test Summary Prod DAT Location Code
Formuln 5 7 10 14 16 30 42 Weed St Louis F1M 18 + 0.5 70 100 100
Poison Ivy St Louis F1M 18 + 0.5 85 100 100 Fesc/Blue St Louis F1M
18 + 0.5 35 85 100 Golden Rod St Louis F1M 18 + 0.5 50 100 100
Fesc/Blue Miss F1M 18 + 0.5 37 80 100 Kudzu Clem F1M 18 + 0.5 80
Poison Ivy 60 96.3 St Louis F2M 18 + 1 80 100 100 Poison Ivy St
Louis F2M 18 + 1 80 100 100 Feso/Blue St Louis F2M 18 + 1 65 88 98
Golden Rod St Louis F2M 18 + 1 70 100 100 Fesc/Blue Miss F2M 18 + 1
45 87 100 Kudzu Clem F2M 18 + 1 91.6 Poison Ivy 74 97 St Louis F3M
18 + 2 90 100 100 Poison Ivy St Louis F3M 18 + 2 85 100 100
Fesc/BIue St Louis F3M 18 + 2 80 98 100 Golden Rod St Louis F3M 18
+ 2 80 100 100 Fesc/Blue Miss F3M 18 + 2 37 73 98 Kudzu Clem F3M 18
+ 2 100 Poison Ivy 84 99.5 St Louis F4C 18 + 3 95 100 100 Poison
Ivy St Louis F4C 18 + 3 90 100 100 Fesc/Blue St Louis F4C 18 + 3 90
98 98 Golden Rod St Louis F4C 18 + 3 70 100 100 Fesc/Blue Miss F4C
18 + 3 47 78 100 Kudzu Clem F4C 18 + 3 100 Poison Ivy 86 99.5 St
Louis RU1 27% 50 95 100 Poison Ivy R'up Brush St Louis RU1 27% 50
95 100 Fesc/Blue R'up Brush St Louis RU1 27% 50 95 95 GoldenRod
R'up Brush St Louis RU1 27% 85 98 98 Fesc/Blue R'up Brush Miss RU1
27% 42 83 100 Kudzu R'up Brush Clem RU1 27% 80 Poison Ivy R'up
Brush 59 95.8 St Louis BBG Brush- 85 100 100 Poison Ivy B-Gon St
Louis BBG Brush- 50 65 70 Fesc/Blue B-Gon St Louis BBG Brush- 40 65
65 Golden Rod B-Gon St Louis BBG Brush- 0 0 0 Fesc/Blue B-Gone Miss
BBG Brush- 33 23 73 Kudzu B-Gone Clem BG Brush- 70 Poison Ivy
B-Gone 44 57.5 Miss BBG + FS1 Brush- 40 30 85 Kudzu B-Gone + Clem
BBG + FS1 Brush- 86.4 Poison Ivy B-Gone + St Louis ENF Enforcer 85
100 100 Poison Ivy St Louis ENF Enforcer 20 15 0 Fesc/Blue St Louis
ENF Enforcer 30 75 75 Golden Rod St Louis ENF Enforcer 0 0 0
Fesc/Blue 34 47.5 Product 5 7 10 14 16 30 42 Code DAT DAT DAT DAT
DAT DAT DAT Weed BBG 85 100 100 Poison Ivy BBG 50 65 70 Fesc/Blue
BBG 40 65 65 Golden Rod BBG 0 0 0 Fesc/Blue BBG 33 23 73 Kudzu BBG
70 Poison Ivy RU1 50 95 100 Poison Ivy RU1 50 95 100 Fesc/Blue RU1
50 95 95 Golden Rod RU1 85 98 98 Fesc/Blue RU1 42 83 100 Kudzu RU1
80 Poison Ivy F3M 90 100 100 Poison Ivy F3M 85 100 100 Fesc/Blue
F3M 80 98 100 Golden Rod F3M 80 100 100 Fesc/Blue F3M 37 73 98
Kudzu F3M 100 Poison Ivy
Example 5
Additional Field Test in St. Louis
[0220] Following the procedures set forth in Example 4, additonal
fields tests were carried in the St. Louis area in July of 2003, in
order to further evaluate the performance of various formulations
on poison ivy, as well as all weeds present. (See Tables 1.1, 1.2
and 3 for additioanl details on product formulations.) The results
of these tests are presented in Table 5, below.
23TABLE 5 Summary of Test Results Poison Ivy Total weed % injury %
injury Formuln Rate in 6 12 6 12 Code Formln oz/1 gallon DAT DAT
DAT DAT SBK Super BK 32 3.2 60 90 50 65 SPC Spectra conc 5 70 94 70
80 ENF Enforcer 2.56 65 90 55 60 BBG Brush-B-Gon 4 60 85 55 60 F3M
18 + 2 6 90 100 90 96 F5M 1 + 0.1 RTU 85 100 85 96 RUP R'up RTU RTU
80 99 80 94 RU1 27% R'up Brush 6 90 90 80 85
* * * * *