U.S. patent application number 11/597149 was filed with the patent office on 2008-02-14 for stable and water-soluble plant growth regulator liquid compositions and methods for use of same.
Invention is credited to Bruce Baldi, Mark Beach, Gregory Clarke, Bruce Kirkpatrick, John Lopez, Yueh Wang, Prem Warrior.
Application Number | 20080039322 11/597149 |
Document ID | / |
Family ID | 35450592 |
Filed Date | 2008-02-14 |
United States Patent
Application |
20080039322 |
Kind Code |
A1 |
Wang; Yueh ; et al. |
February 14, 2008 |
Stable and Water-Soluble Plant Growth Regulator Liquid Compositions
and Methods for Use of Same
Abstract
Soluble and stable liquid compositions containing a plant growth
regulator selected from the group consisting of cytokinin and a
gibberellin, an acid solubilizer such as citric acid, tartaric acid
or glycolic acid and a solvent; as well as methods for making and
using the composition are disclosed. The compositions improve
solubility, handling, stability, safety, as well as activity
improvements such as improved plant growth, yield, fruit thinning
or sizing and quality. The compositions are soluble and stable by
adding an ethoxylated alkyl alcohol wherein the growth regulator is
6-benzyladenine (6-BA) or forchlorfenuron (CPPU) and the
ethoxylated alcohol surfactant is C12-15 alkyl alcohol in propylene
glycol. The compositions may also contain a cytokinin such as
6-benzyladenine (6-BA) or forchlorfenuron (CPPU) that is increased
in solubility and activity and by synergistically combined with
GA.sub.3 or GA.sub.4A.sub.7 as well as in storage stability by
adding an antioxidant. The compositions are formulated in a
ready-to-mix formulation.
Inventors: |
Wang; Yueh; (Arlington
Heights, IL) ; Beach; Mark; (Bristol, WI) ;
Kirkpatrick; Bruce; (Murdelein, IL) ; Clarke;
Gregory; (Dillsburg, PA) ; Lopez; John;
(Gurnee, IL) ; Warrior; Prem; (Green Oaks, IL)
; Baldi; Bruce; (Libertyville, IL) |
Correspondence
Address: |
WOOD, PHILLIPS, KATZ, CLARK & MORTIMER
500 W. MADISON STREET
SUITE 3800
CHICAGO
IL
60661
US
|
Family ID: |
35450592 |
Appl. No.: |
11/597149 |
Filed: |
May 23, 2005 |
PCT Filed: |
May 23, 2005 |
PCT NO: |
PCT/US05/17909 |
371 Date: |
October 26, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60574354 |
May 24, 2004 |
|
|
|
Current U.S.
Class: |
504/136 ;
504/260 |
Current CPC
Class: |
A01N 43/90 20130101;
A01N 43/90 20130101; A01N 25/04 20130101; A01N 43/90 20130101; A01N
47/36 20130101; A01N 47/36 20130101; A01N 43/90 20130101; A01N
43/90 20130101; A01N 25/30 20130101; A01N 47/36 20130101; A01N
45/00 20130101; A01N 43/90 20130101; A01N 45/00 20130101; A01N
2300/00 20130101; A01N 45/00 20130101; A01N 45/00 20130101; A01N
25/30 20130101; A01N 2300/00 20130101; A01N 43/90 20130101; A01N
47/36 20130101; A01N 25/02 20130101; A01N 47/36 20130101; A01N
25/04 20130101; A01N 25/02 20130101 |
Class at
Publication: |
504/136 ;
504/260 |
International
Class: |
A01N 43/54 20060101
A01N043/54; A01N 43/40 20060101 A01N043/40; A01P 21/00 20060101
A01P021/00 |
Claims
1. A composition comprising a plant growth regulator and an acid
solubilizer selected from the group consisting of citric acid,
tartaric acid and glycolic acid.
2. The composition of claim 1 wherein the plant growth regulator is
selected from the group consisting of gibberellins, auxins,
cytokinins, organic acids, ethylene biosynthesis inhibitors and
combinations thereof.
3. The composition of claim 2 wherein the plant growth regulator is
cytokinin or cytokinin and gibberelin combinations.
4. The composition of claim 3 wherein the cytokinin is selected
from the group consisting of 6-benzyl adenine and forchlorfenuron
and the gibberellin is GA3 or GA4A7.
5. The composition of claim 1 further comprising a solvent.
6. The composition of claim 5 wherein the solvent is a propylene
glycol.
7. The composition of claim 1 further comprising an
antioxidant.
8. The composition of claim 7 wherein the antioxidant is selected
from the group consisting of propyl gallate, ethoxyquin, butylated
hydroxyanisole, butylated hydroxytoluene and tertiary
butylhydroquinone.
9. The composition of claim 1 further comprising at least one
surfactant.
10. The composition of claim 9 wherein the surfactant is selected
from the group consisting of ethoxylated alkyl alcohols, dioctyl
sodium sulfosuccinates, ethoxylated fatty acids, ethoxylated
vegetable oils, glycol esters, sorbitan fatty acid esters,
ethoxylated sorbitan fatty acid esters and combinations
thereof.
11. The composition of claim 1 wherein the plant growth regulator
is benzyadenine and the solubilizer is anhydrous citric acid.
12. The composition of claim 1 wherein said composition is diluted
in water.
13. A composition comprising benzyadenine, anhydrous citric acid,
ethoxylated alcohols, propyl gallate and propylene glycol.
14. The composition of claim 13 having from about 1.5 to about 3.0
weight percent 6-benzyladenine, from about 1.5 to about 3.0 weight
percent anhydrous citric acid, from about 3.5 to about 5.5 weight
percent ethoxylated alcohols, from about 0.05 to about 0.20 weight
percent propyl gallate and from about 91.00 to about 93.00 weight
percent propylene glycol.
15. The composition of claim 14 having about 1.93 weight percent
6-benzyladenine, about 2.0 weight percent anhydrous citric acid,
about 4.0 weight percent ethoxylated alkyl alcohols, about 0.1
weight percent propyl gallate and about 91.97 weight percent
propylene glycol.
16. A ready-to-mix formulation comprising the an inert composition
comprising the composition of claim 15.
17. The ready-to-mix formulation of claim 16 further comprising an
insecticide, a herbicide, a fungicide, or combinations thereof.
18. A method of regulating plant growth comprising the step of
treating a seed, soil or a plant with an effective
growth-regulating amount of a composition of claim 1.
19. The method of claim 18 wherein said plant is a fruit-producing
plant.
20. The method of claim 19 wherein said fruit-producing plant is
selected from the group consisting of grapes, apples, pistachio,
cherries, lemons, limes, oranges and tangerines.
21. The method of claim 18 wherein said composition is diluted with
water and spray applied.
22. The method of claim 21 wherein said composition is diluted with
water and spray applied.
23. A method of preparing a soluble liquid plant growth regulator
formulation comprising the step of: mixing a plant growth regulator
with a acid solubilizer selected from the group consisting of
citric acid, tartaric acid and glycolic acid, an antioxidant and
solvent to produce a homogeneous mixture.
24. A composition comprising a plant growth regulator and an
ethoxylated alcohol surfactant and a solvent.
25. The composition of claim 24 wherein the plant growth regulator
is forchlorfenuron and the ethoxylated alcohol surfactant is C12-15
alkyl alcohol and the solvent is propylene glycol.
26. The composition of claim 25 further comprising anhydrous citric
acid.
27. The composition of claim 26, wherein the forchlorfenuron is
from about 0.5 to 2.0 weight percent, the anhydrous citric acid is
from about 0.5 to about 2.0 weight percent, the C12-15 alkyl
alcohol is from about 1.0 to about 3.0 weight percent and the
propylene glycol is from about 93.0 to about 98.0 weight
percent.
28. The composition of claim 27, wherein the forchlorfenuron is
about 0.84 weight percent, the anhydrous citric acid is about 0.5
weight percent, the C12-15 alkyl alcohol is about 1.0 weight
percent and the propylene glycol is about 97.66 weight percent.
Description
FIELD OF THE INVENTION
[0001] The present invention is directed to soluble and stable
liquid compositions including at least one plant growth regulator,
at least one acid solubilizer, at least one surfactant adjuvant,
and at least one solvent; as well as methods for making and using
the compositions. The soluble liquid composition advantageously
improves the preparation, the storage stability, the handler safety
and the performance of a plant growth regulator formulation for
spray application, as such composition is highly soluble in use
dilutions, is easily metered, can be more highly concentrated and
is dust-free. A presently preferred soluble liquid composition
includes at least one plant growth regulator selected from the
group consisting of an adenine cytokinin, an acid solubilizer
selected from the group consisting of citric acid, tartaric acid
and glycolic acid, a dilution solubilizer comprising a nonionic
and/or anionic surfactant blend and a solvent comprising propylene
glycol. The growth regular is preferably 6-benzyladenine
(6-BA).
[0002] The present invention is also directed to soluble and stable
liquid compositions comprising at least one plant growth regulator
selected from the group consisting of a phenylurea cytokinin, a
dilution solubilizer comprising nonionic and/or anionic surfactant
blend and a solvent comprising propylene glycol. The growth
regulator is preferably forchlorfenuron (CPPU) and the nonionic
surfactant is preferably ethoxylated C12-15 alkyl alcohols.
[0003] The present invention is also directed to obtaining a
synergistic effect by combining cytokinin and gibberellin plant
growth regulators such as 6-BA and/or CPPU with GA.sub.3 or
GA.sub.4A.sub.7.
BACKGROUND OF THE INVENTION
[0004] Plant growth regulators are useful for influencing a range
of plant developmental processes including stem elongation,
germination, dormancy, flowering, sex expression, enzyme induction,
fruit size and quality, as well as leaf and fruit senescence. Plant
growth regulators may be formulated in at least five different
types of formulations: 1) solutions, 2) wettable powders, 3)
soluble powders, 4) tablets, and 5) water-soluble or dispersible
granules. In order to use such formulations, they must be diluted
in an aqueous solution prior to conventional spray application.
Each of the conventional types of formulations has disadvantages,
so research to provide improved plant growth regulator formulations
continues. The disadvantages of the conventional formulations will
be discussed with reference to two important plant growth regulator
classes, the gibberellins and the cytokinins, as representative of
conventional formulations of plant growth regulators in
general.
[0005] Gibberellins are one class of plant growth regulators which
are diterpenoid acids. Gibberellins are commercially produced by
fermentation of a natural fungus, Gibberella fugikuroi.
Gibberellins are marketed under various trade names and are
commercially used on a variety of fruit orchards, vegetable crops,
row crops, and ornamental crops. The predominantly used gibberellic
acid is GA.sub.3, formulated in any of the five forms described
above. The other commonly used gibberellins are a combination of
two, (GA.sub.4+7) which are primarily formulated as solutions in
isopropyl alcohol, tetrahydrofurfuryl alcohol (THFA) or propylene
glycol. Due to diterpenoid structure of gibberellins containing
double bonds and cyclic lactone, they are less stable in liquid
form, especially in water.
[0006] Cytokinins are another class of plant growth regulators
which are generally defined as N6-substituted adenine derivatives
such as trans-zeatin, 6-benzyladenine and kinetin. Recently, a new
class of cytokinins has been identified and they possess
N-phenylurea substituted structure such as forchlorfenuron (CPPU)
and thidiazuron (TDZ). Cytokinins are of extreme importance in
regulating plant growth and development, especially cell division.
They are marketed under various trade names and are commercially
used in fruit thinning and sizing as well as pre- and post-harvest
treatments of ornamental plants and flowers. Cytokinins have low
solubility in water or solvent and solubility improvement in
formulation and in use dilution are important for obtaining their
biological effectiveness.
Solution Formulations
[0007] Gibberellin and cytokinin solution formulations are
disadvantageous in several respects. The solutions, such as those
of 6-BA in propylene glycol or THFA, are less concentrated due to
low solubility of actives, and GA4+A7 have limited stability due to
oxidation or chemical degradation. The result is that current
GA4+A7 products have a limited shelf life due to 10-15% loss per
year. Overformulation and rework are then required for aged product
in order to meet label claim. Of the currently used solvents,
isopropyl alcohol and methyl alcohol offer severe disadvantages
such as flammability and toxicity, which lead to restrictions in
manufacturing, packaging, labeling, transportation, and warehousing
of such solutions. A more powerful THFA solvent has to be used in
some of the 6-BA formulations, however, THFA is considered
corrosive to the eye and skin. Moreover, low solubility of
cytokinins in propylene glycol does not permit preparation of high
potency solution formulations. These low strength solution
formulations also require larger packaging, more storage space, and
higher associated transportation, warehousing, and container
disposal costs. Due to very low solubility and undesirable
hydrolysis, it has not been possible to formulate gibberellins or
cytokinins in aqueous systems. Some examples of solution
formulations of gibberellins include PROGIBB 4%.RTM., PROVIDE.RTM.,
PROCONE.RTM., RALEX.RTM., RELEASE LC.RTM. and RYZUP.RTM.,
cytokinins include ACCEL.RTM., and REGULEX.RTM., and gibberellin
and cytokinin combinations include PROMALIN.RTM., all available
from Valent BioSciences Corp.
Powder Formulations
[0008] A soluble powder formulation is one which, when mixed with
water, dissolves readily in water and forms a true solution. Once
the solution is formed, no further mixing or agitation of the
tank-mix is required. Mixing is a process of combining different
materials, usually to a homogeneous state. Agitation aids the
process of mixing, and is a mechanical process involving rotating
shafts of blades in the bottom of the spray tank.
[0009] An example of a powder gibberellin formulation is PROGIBB
2X.RTM., available from Valent BioSciences Corp., which contains
20% by weight of the active ingredient, gibberellin. A wettable
powder formulation is a dry, finely ground formulation. In this
formulation, the active ingredient is combined with a finely ground
dry carrier, usually a mineral clay, along with other ingredients
that enhance the ability of the powder to be suspended in water.
Upon mixing the wettable powder with water, a suspension is formed,
which is then applied by a spray technique. Examples of a wettable
powder gibberellin formulation include PROGIBB PLUS.RTM., ACTIVOL
10%.RTM. and RELEASE.RTM., all available from Valent BioSciences
Corp.
[0010] The primary disadvantage of wettable powder and soluble
powder formulations is that they tend to produce dust upon
handling, such as when pouring, transferring or measuring them.
This dust may pose health hazards. Further, powder formulations
tend to wet poorly and also solubilize slowly upon addition to
water. Powder formulations thus take longer times to wet, disperse
and solubilize in the tank-mix. Formation of lumps or partially
solubilized spray solutions will lead to uneven distribution of the
plant growth regulator in the tank-mix with potential for reduced
field performance. Sometimes, foam in the spray tank caused by
spray tank adjuvants can also affect wetting and solubility of
wettable and soluble powders. Wettable powder formulations will
also leave undesirable insoluble residues both in the tank and on
the sprayed foliage and fruit. For insoluble cytokinins, the
wettable powder formulations of large particle size are ineffective
as plant growth regulators.
Tablet Formulations
[0011] Tablet formulations are pre-measured dosage delivery
systems. They are useful in small areas, or for ornamental
purposes. Tablet formulations may be effervescent, which dissolve
in water over a period of two to ten minutes depending upon the
type and size of the tablet. However, tablets deliver only between
0.1-1 gram of active ingredient per tablet. They are not ideal for
large-scale field operations. Moreover, effervescent tablets are
highly susceptible to humidity, may be slow to dissolve and are
expensive.
Water-Soluble or Dispersible Granules
[0012] Water-soluble or water-dispersible granules are also known
as soluble or wettable granules. This type of formulation is
similar to a wettable powder, except that the active ingredient is
formulated as granular particles of 100 to 300 micron size. To
prepare the water-soluble or dispersible granules for spray
application, they are completely soluble or dispersable in water
upon agitation. Many different water-soluble or water-dispersible
granular formulations are known for agricultural chemicals. For
example, EP 0 252 897 and U.S. Pat. No. 4,936,901 disclose
encapsulated plant growth regulators in water dispersible granular
formulations, U.S. Pat. No. 6,387,388 B1 and U.S. Patent
Application Publication US 2002/0114821 A1 disclose an extruded
water-soluble insecticide, and U.S. Pat. No. 5,622,658 discloses an
extrudable composition for preparing water-dispersible granules. An
example of a granular gibberellin formulation containing 3.1%
active ingredient is Gibberellin Kyowa Soluble Powder, available
from Kyowa Fermentation Industry of Japan.
[0013] Water-soluble or dispersible granules usually have no
greater than eight percent moisture content, and form solution or
suspensions when added to aqueous solutions. The quality of
water-soluble or water-dispersible granules is highly process- and
active-ingredient-dependent, and can result in low yield
recoveries, poor attrition resistance leading to dust potential,
high manufacturing cost and poor dispersion. Generally, sprays of
dissolved water-dispersible granular formulations leave undesirable
insoluble residues on the treated foliage and fruit.
[0014] For plant growth regulators such as gibberellins or
cytokinins to be efficacious, the active ingredient must be
solubilized in the tank-mixes prior to application. In addition,
water-soluble or -dispersible granules can become hardened over
time and thus result in poor solubility or dispersibility of the
active ingredient. Dust and caking may be problems with certain
water-soluble or water-dispersible granules and powder
formulations.
[0015] Even with liquid formulations, due to poor water and solvent
solubility of plant growth regulators such as 6-benzyl adenine and
forchlorfenuron (CPPU), THFA is required to be used as a solvent
and precipitation or crystallization of active ingredients can
occur in field-tank mixing, which will have an adverse effect on
the plant growth regulator activity and the handling of a toxic
THFA product.
[0016] Therefore, a plant growth regulator formulation which
provides high potency, product safety, stability and solubility,
and avoids the problems associated with conventional formulations,
would be advantageous.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1. shows the improved 6-BA uptake of representative
compositions of the present invention in comparison with other
compositions.
BRIEF SUMMARY OF THE INVENTION
[0018] The present invention is directed to a novel plant growth
regulator composition in a concentrated liquid form, as well as
methods for making and using the composition. The invention
improves a plant growth regulator that is normally insoluble such
as 6-benzyladenine (6-BA) or forchlorfenuron (CPPU) by making it
more soluble, as well as utilizing its synergistic characteristics
by combining it with gibberellins such as GA.sub.3 and less stable
GA.sub.4A.sub.7 (GA.sub.4+7). The composition comprises at least
one plant growth regulator and at least one acid solubilizer
selected from the group consisting of citric acid, tartaric acid
and glycolic acid. The composition preferably includes at least one
solvent and one surfactant. The liquid composition advantageously
improves handler safety, preparation, penetration and storage
stability of a plant growth regulator formulation for spray
application, as such composition swiftly dissolves or is highly
soluble, is easily metered, can be more highly concentrated and is
dust-free for handling. Preferably the plant growth regulator is
selected from the group consisting of gibberellins, auxins,
cytokinins, organic acids, ethylene biosynthesis inhibitors, and
combinations thereof. More preferably, the plant growth regulator
is a cytokinin and/or a gibberelin. Most preferably, the plant
growth regulator is 6-benzyl adenine or forchlorfenuron (CPPU).
[0019] In another embodiment, the composition comprises at least
one plant growth regulator and an ethoxylated alkyl alcohol
surfactant. The growth regulator is preferably forchlorfenuron
(CPPU) and the ethoxylated alkyl alcohol surfactant is a C12-15
alcohol in propylene glycol solvent.
[0020] Additionally, the composition may further comprise an
antioxidant. The antioxidant may be propyl gallate, ethoxyquin,
butylated hydroxyanisole, butylated hydroxytoluene, tertiary
butylhydroquinone and combinations thereof. The surfactant may be
ethoxylated alcohols, dioctyl sodium sulfosuccinates, ethoxylated
fatty acids, ethoxylated vegetable oils, glycol esters, sorbitan
fatty acid esters, and ethoxylated sorbitan fatty acid esters and
combinations thereof.
[0021] The composition may also contain at least one additional
component such as a cosolvent (ethyl lactate, butyl lactate, methyl
fatty ester or acetyltributyl citrate, all EPA list 4 inerts), a
sticker, a spreader sticker, a systemic acquired resistance
inducer, an anti-foaming agent, a preservative, a humectant, a dye,
a U.V. protectant, a buffer, a carrier or a combination
thereof.
[0022] The preferred formulation of the composition comprises
benzyadenine, anhydrous citric acid, ethoxylated C12-15 alcohols,
propyl gallate and propylene glycol. The preferred weight range of
the formulation is from about 1.5 to about 3.0 weight percent
6-benzyladenine, from about 1.5 to about 3.0 weight percent
anhydrous citric acid, from about 3.5 to about 5.5 weight percent
ethoxylated C12-15 alcohols, from about 0.05 to about 0.20 weight
percent propyl gallate and from about 91.00 to about 93.00 weight
percent propylene glycol.
[0023] The invention is also directed to a method of regulating
plant growth comprising the step of treating soil, a seed or a
plant with an effective growth-regulating amount of the composition
described above. The composition of the present invention may be
formulated as a ready-to-mix formulation that is diluted in water
and spray-applied in order to improve plant growth, yield, fruit
thinning, fruit sizing, flowering and quality. The plant is
preferably a fruit bearing plant, as for example one that produces
grapes, apples, pears, peaches, cherries, lemons, limes, oranges,
pistachio or tangerines.
[0024] The invention is also directed to a method of preparing a
soluble liquid plant growth regulator formulation comprising the
steps of mixing the plant growth regulator, acid solubilizer,
surfactant, antioxidant and solvent to produce a final soluble
liquid composition. In the method, preparation of the formulation
for spray application can be enhanced, since the solubilizer and
the surfactant produce clear spray solution of micro- or
nano-particle size and prevent the crystallization of insoluble
active ingredient in use dilution, and accurate metering and rapid
dissolution of the composition can be attained. The formulation of
the present invention is high in product solubility, handling
safety, storage stability, and improves plant growth, yield, fruit
thinning or sizing and quality. The ready-to-mix compositions can
be used for liquid insecticide, herbicide and fungicide
formulations.
DETAILED DESCRIPTION OF THE INVENTION
[0025] We have now surprisingly discovered that highly
concentrated, soluble and stable liquid formulations of plant
growth regulators are improved if organic acid solubilizers such as
citric acid, tartaric acid or glycolic acid are added to the
composition and dilution solubility is improved if an ethoxylated
alkyl alcohol surfactant is added to the composition. The
composition having improved dilution solubility preferably
comprises 6-BA or CPPU as the plant growth regulator and propylene
glycol as the solvent and the ethoxylated C12-15 alcohol as the
surfactant. The acid solubilizer prevents crystallization of the
active ingredient at ambient or cold storage temperature thereby
resulting in a more concentrated liquid formulation. The soluble
liquid formulation is still safe, stable and effective.
[0026] The phrase "plant growth regulator" as used herein connotes
a product which serves to modify the growth and the development of
a treated plant to agricultural maturity without killing the plant.
Such modification may result from the effect of the material on the
physiological processes of the plant, or from the effect of said
material on the morphology of the plant. These modifications may
also result from any combination or sequence of physiological or
morphological factors.
[0027] The plant growth regulator may be a gibberellin, an auxin,
an organic acid, a cytokinin, an ethylene biosynthesis inhibitor,
or a combination thereof. Suitable ethylene biosynthesis inhibitors
include aminoethoxyvinylglycine; suitable auxins include
indole-3-acetic acid and indole butyric acid; suitable organic
acids include a-naphthyl acetic acid and suitable cytokinins
include 6-benzyladenine or 6-benzylaminopurine (6-BA),
forchlorfenuron (CPPU), thidiazuron (TDZ) and 6-furfurylaminopurine
(kinetin).
[0028] In the formulation of the present invention, a surfactant
may be used as a wetting, solubilizing and penetrating agent for
certain plant growth regulators. Suitable surfactants include
non-ionic surfactants, anionic surfactants and amphoteric
surfactants. Non-ionic surfactants include ethoxylated alkyl
alcohols such as TOMADOLS.RTM., ethoxylated vegetable oils such as
AGNIQUE SBO.RTM. (soybean), CSO (castor) and RSO (rapeseed),
ethoxylated sorbitan esters such as EMSORB.RTM., TWEEN.RTM., and
T-MAZE.RTM.; sorbitan fatty acid esters such as SPAN.RTM. and
ALKAMUL.RTM.; sucrose and glucose esters and derivatives thereof
such as MAZON.RTM., RHEOZAN.RTM. and GLUCOPON.RTM.; ethoxylated
alcohols such as TRYCOL.RTM., BRIJ.RTM., ARMIX.RTM., TERGITOL.RTM.
and PLURAFAC.RTM.; ethoxylated alkylphenols such as IGEPAL.RTM.,
MACOL.RTM. and TRITON.RTM.; ethoxylated fatty amines such as
TRYMEEN.RTM. and ETHOMEEN.RTM.; ethoxylated fatty acids such as
EMEREST.RTM., ALKAMUL.RTM. and TRYDET.RTM.; ethoxylated fatty
esters such as ALKAMUL.RTM. and ATLAS G.RTM.; fatty acids such as
ATLAS G-1556.RTM.; glycerol esters such as MAZOL GMO.RTM.; glycol
esters such as GLYCOL SEG.RTM.; lanolin-based derivatives such as
AMERCHOL CAB.RTM.; methyl esters such as OLEOCAL ME.RTM.;
monoglycerides and derivatives such as ETHOSPERSE G-26.RTM.;
propoxylated and ethoxylated fatty acids such as ANTAROX
AA-60.RTM.; block copolymers of ethylene oxide and propylene oxide
such as PLURONIC.RTM. or SURFONIC.RTM.; silicone-based surfactants
such as SILWET.RTM., BREAKTHRU.RTM. and mixtures of organosilicon
surfactant with non-ionic or ionic surfactants; polysaccharides,
copolymers of acrylamide and acrylic acid; and acetylenic diol
derivatives such as SURFYNOL 104.RTM. or tristyrylphenols such as
SOPROPHOR.RTM. among others.
[0029] A presently preferred nonionic surfactant family is the
ethoxylated alkyl alcohols of C9 to C15 chains (TOMADOL 25-7, 1-7
or 91-6.RTM.). Non-ionic surfactants such as natural ethoxylated
alcohols (BRIJ.RTM.) and vegetable oils (AGNIQUE.RTM.) are
presently also preferred. Suitable anionic surfactants include
phosphate esters such as EMPHOS.RTM. and RHODAFAC.RTM.; dialkyl
sulfosuccinates such as MONAWET.RTM., N-acyl ED3A chelating
surfactant (Hampshire) and N-Acyl Sarcosines (Hamposyl) among
others.
[0030] The tradenames used above of surfactants often are common to
a class or series of surfactants. Therefore, where a tradename is
mentioned, any surfactant in the family including that tradename
will be suitable.
[0031] Other components of the formulation may include additional
surface active agents, cosolvent, dyes, U.V. (ultra-violet)
protectants, antioxidants, antifoams or other components which
facilitate product handling and application.
[0032] It is also contemplated that the ready-to-mix compositions
of this invention may be used in other active ingredients, such as
herbicides, fungicides, insecticides, nematicides, biochemical
pesticides, plant produced pesticides (botanicals) or plant
nutrients.
[0033] A presently preferred composition contains technical grade
active ingredient gibberellin. A preferred technical grade active
ingredient gibberellin is GA.sub.3, since it is the most widely
used plant growth regulator for agriculture, although other
gibberellins, including but not limited to GA.sub.4, or GA.sub.7,
GA.sub.4A.sub.7, and combinations of GA3 or GA4A7 with 6-BA or
CPPU.
[0034] A presently preferred composition includes from about 1.5 to
about 3.0 weight percent 6-benzyladenine, from about 1.5 to about
3.0 weight percent anhydrous citric acid, from about 3.5 to about
5.5 weight percent ethoxylated C12-15 alcohols, from about 0.05 to
about 0.20 weight percent propyl gallate and from about 91.00 to
about 93.00 weight percent propylene glycol.
[0035] A presently preferred composition includes from about 0.5 to
about 2.0 weight percent CPPU, from about 0.5 to about 2.0 weight
percent anhydrous citric acid, from about 1.0 to 3.0 weight percent
ethoxylated C12-15 alcohols and from about 93.0 to 98.0 weight
percent propylene glycol.
The Methods of Use
[0036] Gibberellins are known plant growth regulators. For example,
U.S. Pat. No. 4,242,120 discloses a non-spray combination of a
gibberellin with a low molecular weight carbohydrate such as
saccharide, glucose, fructose or maltose to stimulate
fructification; and U.S. Pat. No. 5,163,993 discloses a combination
of gibberellin and a surfactant for thinning grape clusters.
[0037] The formulations described above may be used to regulate
plant growth of fruit-producing plants, vegetable-producing plants,
row crops, vegetable crops, grasses or trees. The benefits of the
use of the formulation vary, according to the type of fruit
treated. For example, in grapes, treatment with the formulation can
lead to cluster elongation, thinning and larger grapes. In oranges,
lemons, limes and tangerines, the formulation can lead to a delay
the aging of the rind and reduce disorders such as rind staining,
water spotting, sticky or tacky surface, puffy rind or rupture
under pressure. In cherries, the formulation may advantageously be
used to produce larger, brighter colored and/or firmer fruit.
[0038] The formulation is preferably diluted in water and sprayed
on the plant or tree to be treated. The spraying may be by
conventional ground or aerial application equipment. Spray volumes
are variable depending upon the orchard or crop, growth stage and
climatic conditions. The range may be 5 gallons to 300 gallons/acre
or higher. A presently preferred range is between 100 to 250
gallons per acre by pressurized spray application equipment. To
prepare a formulation for application, a tank is half-filled with
water, followed by spray addition of adjuvant, and then addition of
plant growth regulator, followed by addition of more water and
mixing for at least 15 minutes prior to actual spraying.
[0039] Alternatively, the formulation may be directly applied to
the soil (in which the plant will be grown or is growing) with or
without granular fertilizers for the improved growth and
maintenance of crops.
[0040] Moreover, the formulation may be applied to seeds to achieve
the same effect. The seed may be rice or paddy, alfalfa, cotton,
sorghum, soybeans, corn or other vegetables, ornamental or turf and
pasture grass seed, among others.
[0041] The concentration of the plant growth regulator will vary
depending upon the type of fruit is to be treated, the
peculiarities of the locale, and the desired result. In general,
the composition may be applied at a field rate of from about 0.01
to about 1.0 lb per acre; preferably at a rate of from about 0.02
to about 0.5 lbs per acre and most preferably at a rate of from
about 0.02 to about 0.2 lb/acre. For example, the field spray rates
for apples using 6-BA can be about 38-75 g/100 gallon per acre and
for grapes using CPPU can be about 4-8 g/250 gallon per acre.
[0042] A single application may be enough, though depending upon
the particular fruit and desired results, multiple applications may
be made.
[0043] As used herein the term "plant" includes fruit-producing
plants, vegetable-producing plants, row crops, vegetable crops,
grasses and trees.
[0044] The fruit may be grapes, cherries, lemons, limes, oranges,
grapefruit, strawberries, pineapples, stone fruits, apples, pears,
peaches, blueberries, pistachio or tangerines. The row crop may be
cotton, soybeans, corn, sugar cane or rice, among others. The
vegetable crops may be lettuce, artichokes, celery or peppers among
others. The grasses may be Bahaigrass (Paspalum notatum Flugge),
Bentgrass (Agrostis L.), Bermudagrass (Cynodon dactylon L.),
Carpetgrass (Axonopus affinis Chase), Kentucky bluegrass (Poa
pratensis L.), Canada Blugrass (Poa compressa L.), Buffalograss
(Buchloe dactyloides (Nutt.) Englem.), Fescue grasses (Festuca),
annual Rye grass (Lolium L. multiflorum Lam.), perennial Rye grass
(Lolium perenne L.), Saint augustinegrass (Stenotaphrum secundatum
Kuntze), Japanese lawngrass (Zoysia japinica Steud.),
Centipedegrass (Eremochloa ophiuroides (Munro) Hacck, other turf
grasses for residential or commercial establishments, among
others.
[0045] The invention will be understood more clearly from the
following non-limiting representative examples. Of course, the
present invention is not limited to the particular embodiments and
modes of operation described herein and it is possible to imagine a
number of variations in the details without departing from the
scope of this invention.
[0046] The examples below are presented to describe preferred
embodiments and utilities of the invention and are not meant to
limit the invention unless otherwise stated in the claims appended
hereto.
EXAMPLE 1
[0047] In 500 liter batch size (523 kg by weight), 480.9 kg of
propylene glycol solvent is transferred through a heat exchanger to
a mixing tank and the solvent is heated to 40.degree. C.-45.degree.
C. While in the mixing tank, 10.1 kg of 6-BA tech powder (98.5%
active ingredient), 10.5 kg of citric acid powder and 0.5 kg of
propyl gallate powder (TENOX PG.RTM.) are added. The mixture is
agitated until all of the powders are completely dissolved. 21 kg
of ethoxylated C12-15 alcohol surfactant (TOMADOL 25-7.RTM.) is
then added. Everything is mixed for additional 10-20 minutes to
complete the formulation.
EXAMPLE 2
[0048] Example 2 demonstrates increased solvent solubility of 6-BA
(N-6-benzyladenine) by adding soluble organic acids in propylene
glycol, and improved water dilution stability of 6-BA and CPPU
(Forchlorfenuron or N-(2-chloro-4-pyridinyl)-N-phenylurea) in
formulations with low irritating (skin and eyes) surfactants (alkyl
alcohol ethoxylates or/and dioctyl sodium sulfosuccinate) and
citric acid solubilizer. Soluble, stable, safe and ready-to-mix
formulations were achieved with 6-BA or CPPU and acid/surfactant
combinations as shown in Table 1 below. TABLE-US-00001 TABLE 1
Solvent Solubility of 6-BA and CPPU at 20 C. 100 g Solvent Organic
Acid 6-BA CPPU Propylene Glycol -- 1.5 g -- Propylene Glycol 2 g
Citric 2.4 g -- Propylene Glycol 2 g Tartaric 2.5 g -- Propylene
Glycol -- -- 7 g Propylene Carbonate -- -- 6 g Propylene
Glycol-n-Propyl Ether -- -- 10 g Composition, Storage and Dilution
Stability of VBC-30001 and ABG-3207 Cytokinin Products Ingredients,
wt % VBC-30001 ABG-3207 Function 6-Benzyladenine (98.5%) 1.93 --
Active Forchlorfenuron (96.9%) -- 0.84 Active Citric acid,
anhydrous 2.0 0.5 Solubilizer Alkyl alcohol ethoxylate 4.0 1.0
Solubilizer Propyl gallate 0.1 -- Antioxidant Propylene glycol
91.97 97.66 Solvent *VBC-30001 is 1.9% 6-BA Liquid and ABG-3207 is
.8% CPPU Liquid. Storage Stability 65-022-VB lot 51-004-VB lot
Initial 1.90% 6-BA .87% CPPU 12 mo./25 C 1.89 .84 12 mo/25-40 C
1.88 .89 Dilution stability in 342 ppm hard water at .about.23 C.
Formulation Initial 24 hr VBC-30001 2.5%(450 ppm 6-BA) soluble
(clear) soluble (clear) ABG-3207 2.5% (200 ppm CPPU) soluble (light
blue) soluble (light blue) *Reported solubility of 6-BA and CPPU in
25 C water are 60 and 39 ppm, respectively. Complete solubilization
or submicron suspension (light blue color) of cytokinin is
important for obtaining optimal PGR activity in applications.
[0049] Table 1 shows the solvent solubility of 6-benzyl adenine
(6-BA) and CPPU (forchlorfenuron or
N-(2-chloro-4-pyridinyl)-N-phenylurea) at 20 degrees C. 100 g of
solvent are used. The solvent is either propylene glycol, propylene
carbonate or propylene glycol-n-propyl ether. Only 1.5 g of 6-BA
remains soluble in propylene glycol alone. 2.4 g 6-BA remains
soluble if 2 g of citric acid is added to propylene glycol. 2.5 g
of 6-BA remains soluble if 2 g of tartaric acid is added to
propylene glycol. CPPU remains soluble at 7 g, 6 g and 10 g in
propylene glycol, propylene carbonate and propylene glycol-n-propyl
ether, respectively. Thus, 6-BA solubility is increased by adding
citric acid or tartaric acid in propylene glycol. Formulations
designated VBC-30001 and ABG-3207 contain 6-BA and Forchlorfenuron,
respectively, and citric acid, C12-15 alkyl alcohol ethoxylate,
propyl gallate and propylene glycol. The weight percent of each
component is shown. Storage stability for both formulations
(65-022-VB lot for VBC-30001 and 51-004-VB lot for ABG-3207) is
high after 12 months at 25 degree C. or 25-40 degree C. tropical
conditions. The dilution stability data for both formulations shows
that in 342 ppm hard water at about 23 degrees C., 450 ppm of 6-BA
200 ppm of CPPU remain soluble after 24 hr standing.
[0050] Low skin, eye, sensitization or inhalation toxicity are
shown for ABG-3207 (Category IV) and VBC-30001 (mild skin & eye
irritation, Category III). Both formulations employ EPA list 3 or 4
inerts. No flammable IPA nor toxic THFA solvent is used in these
studies.
[0051] Table 1 also shows a preferred formulation of plant growth
regulator compositions of the present invention. Formulation
designated VBC-30001 contains 1.93 weight percent of benzyladenine
technical (98.5% active ingredient), 2.00 weight percent of citric
acid (solubilizer), 4.00 weight percent ethoxylated alcohols
(surfactant adjuvant), 0.10 weight percent propyl gallate
(antioxidant) and 91.97 weight percent propylene glycol (solvent).
A presently preferred composition includes from about 1.5 to about
3.0 weight percent 6-benzyladenine, from about 1.5 to about 3.0
weight percent anhydrous citric acid, from about 3.5 to about 5.5
weight percent ethoxylated alcohols, from about 0.05 to about 0.20
weight percent propyl gallate and from about 91.00 to about 93.00
weight percent propylene glycol. Formulation designated ABG-3207
contains 0.84 weight percent CPPU technical (96.9% active
ingredient), 0.5 weight percent anhydrous citric acid, 1.0 weight
percent ethoxylated alcohols, and 97.66 weight percent propylene
glycol.
EXAMPLE 3
[0052] TABLE-US-00002 TABLE 2 Activity improvement: 100-150 ppm
6-BA sprays improved apple thinning/sizing without Carbaryl
insecticide (2000 field trials) VBC-30001 Average % Average % Rate
Thinning Increase in Size 100 ppm 25.4 18.5 150 ppm 29.6 18.1
[0053] Table 2 shows the activity improvement of 100 ppm or 150 ppm
6-BA sprays. Both formulations improved apple thinning and sizing
without, SEVIN.RTM. (Carbaryl) insecticides as shown in 2000 field
trials. In a similar study, better grape sizing using formulation
ABG-3207 than other formulations (CPPU technical/IPA) is found.
EXAMPLE 4
[0054] FIG. 1 shows C14 radiolabelled 6-BA uptake from compositions
of the present invention (formulation VBC-30001 is designated as
"B") in apple leaves, was superior to other compositions designated
"A" and "C".
[0055] Equal amounts of composition A, B or C (containing
radiolabelled 6-BA) were individually applied to apple leaves and
the amount uptake was determined from sections of the leaves such
as from discs and strips cut from the leaves after a 24 hour period
of absorption. A control was also compared to compositions A, B and
C. The leaves were rinsed with water and the amount of
radiolabelled 6-BA not absorbed in the leaves were determined and
quantified (left bar designated "Rinses"). The amount of
radiolabelled 6-BA absorbed in the leaves determined from the discs
and strips cut from the leaves were determined and quantified
(right bar designated "Non-Rinse"). Six trials were taken for each
compositions and the control and averaged (except one trial was
dropped from "C" and three trials were dropped from "B"). FIG. 1
shows that the 6-BA of the composition of the present invention,
"B", was absorbed (Non-Rinse) at a significant higher level
compared to that of compositions "A" and "C". The amount of 6-BA of
the composition of the present invention that was not absorbed
(Rinses) was significantly lower than that of the other
compositions.
[0056] It is believed that solubilization of the plant growth
regulator, such as 6-BA and CPPU, with the organic acid, such as
citric acid in conjunction with a surfactant in use dilutions will
generate small particle size (microparticles or nanoparticles) for
improving uptake or penetration. Small particle size of high
dissolution rate is important for activity of water insoluble
active ingredients or drugs.
EXAMPLE 5
[0057] Table 3 below shows potential ready-to-mix plant growth
formulations which including at least a plant growth regulator, an
acid, a surfactant and an antioxidant. Formulation VBC-30009
contains 1.9% 6-BA, 2.0% GA4A7 and 0.45% CPPU. Formulation YW-16-7
contains 4.5% GA.sub.3 and 0.42% CPPU. Formulation YW-16-9 contains
2.1% GA.sub.3 and 1.9% 6-BA. Formulations YW-26-1 and YW-26-5
contain 2.1% CPPU. Formulation YW-16-4 contains 9% GA.sub.3.
Additional adjuvants are shown. These formulations show the
synergistic effect of combining 6-BA and CPPU with GA.sub.3 and
GA.sub.4A.sub.7 as well as the composition comprises an ethoxylated
alkyl alcohol surfactant, organic acid and an antioxidant adjuvants
in propylene glycol solvent. TABLE-US-00003 TABLE 3 Ready-to-mix
PGR formulations and Combinations VBC- YW- YW- YW- YW- YW-
Ingredients, Wt % 30009 16-7 16-9 16-4 26-1 26-5 6-BA tech 1.9 1.9
CPPU tech .45 .42 2.1 2.1 GA4A7 tech 2.0 GA3 tech 4.5 2.1 9.0
Citric acid .5 .5 .5 1.0 1.0 Propyl gallate .05 .1 .1 .2 .05 .05
Alcohol ethoxylate C12-15 7.5 C11 5.0 5.0 5.0 5.0 3.5 Monawet
MO-84R2W 1.5 Propylene Glycol UPS Balance Adjuvants: Nonionic
surfactants: C12-15 and C11 Alkyl alcohol ethoxylates (TOMADOL
.RTM. or NEODOL 25-7 and 1-7 .RTM.). Anionic surfactant: Dioctyl
sodium sulfosuccinate (MONAWET MO-84R2W .RTM.) Antioxidants: Propyl
gallate (TENOX PG .RTM.) or Ethoxyquin Organic acids: Citric,
tartaric or glycolic
EXAMPLE 6
[0058] Table 4 below shows stability improvement of formulations
containing GA.sub.4 and GA.sub.7 with ethoxyquin or propyl gallate
antioxidant in GA4A7 or GA4A7/6-BA or/and CPPU liquid formulations.
Components for the formulations are shown. Storage stability data
shows most formulations containing antioxidant have excellent
storage stability._Significant stability improvement of GA4 and GA7
were achieved by adding 0.05-0.1% propyl gallate or 0.5% ethoxyquin
antioxidant in 4% GA4A7 and 6-BA/CPPU plus 2% GA4A7 liquid
formulations. TABLE-US-00004 TABLE 4 Stability Improvement of GA4A7
Liquid Formulations Ingredients, wt % YW-26-1 -2 -3 -4 YW-24-1 -4
-5 GA4A7 (89.9%) 4.5 4.5 4.5 4.5 2.0 2.0 2.0 (55-412-CD lot)
6-Benzyladenine (98.5%) 1.9 1.9 1.9 Forchlorfenuron (96.9%) .45 .45
.45 Citric acid, Anhydrous .5 .5 .5 .5 Propyl gallate TENOX SI
.RTM. (20% + Citric acid) .5 TENOX PG .RTM. (99.2%) .05 .05
Ethoxyquin Raluquin (96%) .5 Alcohol ethoxylate TOMADOL 25-7 .RTM.
7.5 5.25 Dioctyl sulfosuccnate MONAWET MO-84R2W .RTM. (84%) 2.25
Propylene glycol Balance Storage Stability: Initial assays (wt %)
GA4 -- -- -- 2.9 1.2 -- -- GA7 -- -- -- 1.1 .46 -- -- 8.5 mo.
(25-40 C.) GA4 2.56 2.60 2.81 2.87 1.04 1.27 1.26 Remaining 88% 90%
97% 99% 83% 102% 101% GA7 .84 .63 .89 1.03 .36 .46 .45 Remaining
76% 57% 81% 93% 77% 100% 97%
[0059] All references cited are hereby incorporated by
reference.
[0060] The present invention is illustrated by way of the foregoing
description and examples. The foregoing description is intended as
a non-limiting illustration, since many variations will become
apparent to those skilled in the art in view thereof. It is
intended that all such variations within the scope and spirit of
the appended claims be embraced thereby.
[0061] Changes can be made in the composition, operation and
arrangement of the method of the present invention described herein
without departing from the concept and scope of the invention as
defined in the following claims:
* * * * *