Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02348951 2001-04-26
Improved nutrient mixtures for promoting plant growth and
plant health
The technical teaching described below relates to the field
of the promotion of healthy plant growth. The teaching
according to the invention is intended especially to
support and encourage the natural interaction between two
factors, namely on the one hand promotion of plant growth
and strengthening of the resistance of plants to pathogens,
particularly those responsible for fungal, bacterial and/or
viral diseases, but also sucking pests, on the root and/or
aerial parts of the plants. A further object of the
invention is to be able to use, as nutrients or nutrient
mixtures for achieving this object, components which are at
least substantially based on natural substances and which
do not additionally contaminate the working area in
question. This applies both to the soil and plant regions
and to the human and animal regions in contact therewith,
as well as to the groundwater problem which always has to
be taken into account in connection with agricultural
processes.
The technical teaching described below thus meets a
currently important requirement of the agrobiological and
agrochemical process sector, whereby on the one hand it
becomes possible to optimize the sought-after eco-
industrial results without thereby having to disregard the
economic point of view. Practically all the components of
the multicomponent system used according to the invention
can take the form of chemicals based on natural substances.
On the one hand, the source of these components is healthy
plant growth; on the other hand, for example, main
components formed by marine biology or some other kind of
biology are essential constituents of the multicomponent
mixtures in terms of the invention. The teaching according
to the invention combines natural bound carbon cycles and
utilizes the components isolated therefrom, and appropriate
to the demands according to the invention, for plant
development and the care of healthy plant growth. It is
T
CA 02348951 2001-04-26
2
immediately clear that, precisely in this case of the
natural carbon cycle, not only is additional contamination
ruled out, but positive interventions are enabled which can
help to moderate and reduce the damage already in existence
today.
The teaching of the invention builds on a number of the
Applicant's technical developments, some of which form the
subject of appropriate publications and some of which form
the subject of earlier patent applications. Specific
reference will be made to these principles below. However,
the following will be dealt with first:
Subject of the invention
In a first embodiment, the invention provides the use of
multicomponent nutrient mixtures of at least predominantly
organic origin for the cultivation and care of useful and
ornamental plants by activating the plants' rhizosphere
and/or phyllosphere and hence promoting both plant growth
and plant health in combating pathogens, particularly those
responsible for fungal, bacterial and/or viral diseases,
but also sucking pests, on the root and/or aerial parts of
the plants. The nutrient mixtures used according to the
invention contain the following essential main components:
(a) chitin and/or chitosan of oligomeric and/or polymeric
structure, used in combination with
(b) ecologically compatible surfactant compounds from the
class of the alkyl(poly)glycosides of the O/W type -
hereafter also referred to as "APG compounds" - and
also preferably together with
(c) organic compounds which have lipophilic, saturated
and/or olefinically unsaturated hydrocarbon radicals
with a fatty structure and are both aerobically and
anaerobically degradable.
26-Apr-01 12:66 From-HENKEL/COCNIS CORP, PATENT ~,~?348951 2001-04-26_48 T-682
P.02/02 F-800
S
rn terms of rhp act of the invention, the combination of
the active substances (a1, (b) and, if desired, (c) can be
used in a mixture of all the nutrient components with one
another, but it is dlbv possible to use at leaEt some of
said components at different times. In this last-mentioned
case, 11U1htCVCr , it is necessary to ensure that a suf f i ~i Pn>~
combined action of the sum of all the nutrients can be
achieved in the soil and/or >rhe planz_ This makes it
possible in particular to determine or co-determine L1~C
practicable intervals in cases whprP individual components
of the multieornponent m~.xtures are iuL,cwciuo~d at d~fferenc
times.
The multicomponent mixtures according to the invention are
based Uil Lhe objective especially of influencing anr9
promoting precisely the growth of plant strengthening
~uicrohial populations in the rhizosphere region - i.e. the
root region - but also in the phyllosphere reg~.on - i.e. ~u
2o the ourface of the aerial p~rr_ of the plants and
particularly in the leaf region. Acc~wdimgly, the teaching
according tn rh~e invention provides the introduction of the
multlCOmpOnent mixtures both into the soil region and onto
rhp aerial region of the plants. In principle, these
mulzic~wporient mixtures can be uEed in any forms of
presentation optimi2ed to the particular practical
requirements. Thuc suitable examples are hnr_h flowable and
especially water-dilutable multicomponent mixtures, but
also oolid fo~ns of presentarinn which can be e.g. powders,
granules and the like and optionally in eucaYaulated form.
Details o= the teach nci accowdim to the invenLiorl
Firstly, for a better understanding of the teaching
according tea she invention, a brief Summary will be new hp
given of essential features of the relevant published prlar
art aiic3 the subject of the Applicant ~ s earlier garPnt
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4
applications, already mentioned above, in the field in
question.
DE 44 37 313 describes the use of phosphorus-containing and
nitrogen-containing components selected from the class of
the phospholipids for improving plant growth. Addition of
these phospholipids to the substrate on which the plants
are or will be growing improves the growth of these plants.
It is suggested that this increase in growth is linked to a
stimulation of the microorganisms living in the substrate.
Possible phospholipids are primarily lecithin, lecithin
hydrolyzates and chemically modified lecithins.
WO 93/01150 describes easy-to-handle fertilizer mixtures
for introducing N into plant growth. Together with the
mixtures of fertilizers based on macronutrients and
micronutrients for plant cultivation, said patent provides
the use of water and an oil phase in the presence of W/O
invert emulsifiers. This is said to assure the formation
particularly of pasty mixtures in which the closed oil
phase in the form of a film separates or encloses the
aqueous constituents of the mixture. Oils of vegetable
origin and mineral oil are listed as equivalent oil phases.
German patent application DE 197 O1 127 provides a low-
foaming wetting agent, presented in the form of a highly
concentrated but nevertheless flowable and pourable aqueous
concentrate based on surfactant, for intensifying the
penetration and spreading of water in the region of the
plants' root system when watered, said concentrate
containing alkyl(poly)glycoside compounds of the O/W type -
hereafter also referred to as "APG compounds" - as an
ecologically compatible surfactant component, olefinically
unsaturated alcohols as a foam inhibitor/antifoam and
water-soluble lower alcohols as viscosity regulators.
CA 02348951 2001-04-26
The technical teaching of the Applicant's earlier patent
application DE 197 48 884.6 on the promotion and care of
plant growth by controlling the natural growth processes in
the substrate is based on the idea primarily of promoting,
5 controlling and assuring microbial growth in the soil by
introducing a multicomponent mixture, which is described
below. The disclosure of said earlier patent application
is also incorporated here with the subject of the
disclosure of this invention. The primary promotion of
microbial growth is assured particularly in the rhizosphere
region and hence in the region of the substrate through
which the plants' roots pass, this being the decisive
region for plant growth. The teaching of said earlier
patent application is guided by two ideas of overriding
importance: Together with carriers containing
phosphorus (P) and nitrogen (N) and, if desired, other
plant macronutrients and/or micronutrients, selected
compounds containing hydrocarbon radicals are now
introduced into the soil as additional C sources for the
growth of the microbial flora. At the same time, the
formulation of these growth promoters and their use form
allow their optimized spreading in the root region,
including their introduction into the rhizosphere region of
the substrate. The teaching of said earlier patent
application, on which the teaching of the present
development is ultimately also based, is accordingly
characterized by the introduction of aqueous formulations
containing
- ecologically compatible wetting agents of the O/W type,
together with
- organic compounds which have lipophilic, saturated and/or
olefinically unsaturated hydrocarbon radicals with a
fatty structure and are both aerobically and
anaerobically degradable, as additional C sources for the
growth of the microbial flora,
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6
coupled with the simultaneous and/or staggered introduction
of
- P and/or N compounds, at least some of which have
lipophilic radicals and which are preferably oil-soluble,
and, if desired, carriers containing other macronutrients
and/or micronutrients for plant growth.
Even though such a strengthening of the healthy natural
microbial flora in the soil and hence in particular of
corresponding bacterial strains in the rhizosphere region
of the growing plant enables positive effects to be
achieved in terms of healthy plant growth, the teaching of
this invention now provides a further substantial extension
of the technical possibilities in precisely this field.
It is known from the relevant published prior art that the
concomitant use of chitin and chitin-based derivatives -
especially chitosans in this case - in the agricultural
sector makes it possible to achieve substantial
improvements which are characterized on the one hand by a
strengthening of plant health, but also in particular by an
increase in crop yield. From the comprehensive literature,
reference may be made, for example, to the publication by
Zbigniew S. Karnicki et al. entitled "CHITIN WORLD",
Wirtschaftsverlag NW, Verlag fur neue Wissenschaft GmbH,
Bremerhaven, Germany, 1994. Reference may be made here
e.g. to the section by Henryk Pospieszny et al. entitled
"NEW APPLICATIONS OF CHITOSAN IN AGRICULTURE", loc. cit.,
pages 246 to 254, and the literature cited therein.
Reference may also be made to chapter 8 by Donald Freepons
entitled "Enhancing Food Production with Chitosan Seed-
Coating Technology" and to other sections of the same
literature reference: chapter 1 by Q. Li et al. entitled
"Applications and Properties of Chitosan", chapter 2 by
Shigehiro Hirano entitled "Applications of Chitin and
Chitosan in the Ecological and Environmental Fields" and
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7
chapter 11 by Henryk Struszczyk et al. entitled "New
Applications of Chitin and Its Derivatives in Plant
Protection". Finally, reference may be made to the
publication by Lee A. Hadwiger et al. entitled "CHITOSAN, A
NATURAL REGULATOR IN PLANT-FUNGAL PATHOGEN INTERACTIONS,
INCREASES CROP YIELDS", Academic Press, Inc. 1984, pages
291 et seq., and to the publication in "Biotechnology
Annual Review Volume 2", Elsevier Science B.V. 1996,
entitled "Chitin biotechnology applications", edited by
SHIGEHIRO HIRANO, loc. cit., pages 237 to 258.
The literature cited here shows that the chitin bound to
natural substances, or derivatives thereof, and especially
the chitosan obtained by deacetylation, both in oligomeric
form and in polymeric form, exhibit a pronounced activity
during plant cultivation in the sense of a marked activity
against pathogens, particularly those responsible for
fungal, bacterial and/or viral diseases. However, chitin
or chitosan-based treatment agents also prove to be
effective against sucking pests on the root and/or aerial
parts of the plants. The teaching according to the
invention utilizes this knowledge of the prior art and
combines these components - referred to as active substance
class (a) in the definition according to the invention -
with the nutrients or nutrient mixtures which are
emphasized in the teaching of earlier patent application DE
197 48 884.6 and which are described according to the
invention in subclasses (b) - APG compounds of the O/W type
- and (c) - compounds which have hydrocarbon radicals with
a fatty structure and are both aerobically and
anaerobically degradable. Studies on the significance of
the individual components of the nutrients or active
substances combined according to the invention have shown
that combining components) (a) - i.e. the chitosan
compounds of oligomeric and/or polymeric structure - with
the APG compounds of the O/W type already affords
substantial increases in efficacy in terms of the objective
CA 02348951 2001-04-26
8
according to the invention. The principle here is probably
the very greatly intensified spreading of nutrient
class (a) in the soil structure and hence, in particular,
its introduction into the immediate boundary region of the
root surface, or, where such nutrient mixtures of
components (a) and (b) are applied to the aerial part of
the plants, the likewise intensified spreading of the
chitosan-based nutrient constituents. This is probably
also accompanied by encouragement of the penetration of
these nutrient components into the microstructure of the
plant cuticle and especially the leaf surface. Of course,
the same also applies to the corresponding spreading or
distribution of nutrient components (c) concomitantly used
according to the invention.
In one preferred embodiment, the invention provides, in
addition to components (a), (b) and preferably (c), the
introduction or application of P and/or N compounds, at
least some of which have lipophilic radicals, and, if
desired, carriers containing other macronutrients and/or
micronutrients for plant growth, into the region of the
plants' roots and/or to the aerial part of the plants.
More evidence of the specific nature of nutrients or
nutrient class (d) mentioned here will be given below.
Firstly, however, the following clarification will be
reiterated:
The essence of the improved technical act in terms of the
teaching according to the invention lies in the combination
of these nutrient classes (a), (b) and (c) in terms of the
teaching according to the invention, preferably with the
concomitant use of the nutrients of subclass (d) - P and/or
N compounds having lipophilic radicals. Let it be
emphasized here yet again that each of the nutrient
subclasses in question can be completely and/or
substantially based on natural substances and fully
undergoes natural degradation by metabolic processes.
CA 02348951 2001-04-26
9
Chitin and the chitosan compounds derived therefrom are
known to be natural substances which are formed for example
by marine fauna, especially crabs, crustacea and similar
shellfish, and are obtained as residual substances when
these seafoods are commercially exploited. By combining
them with the other nutrient classes of the teaching of the
invention, which in turn are of vegetable origin, it
becomes possible to optimize healthy plant growth without
having to resort to synthetic auxiliary substances like
fungicides, bactericides, virucides and the like. However,
in the manner known to those skilled in the art, the
biological synthesis of chitin - and hence the preparation
of chitosans in terms of the invention - as part of the
cultivation of fungal populations can also be carried out
on the industrial scale.
Firstly, detailed information on nutrient components (a),
(b), (c) and (d) defined according to the invention will be
given below.
(a) "Chitin and/or chitosan of oliaomeric and/or oolvmeric
structure"
It is known that the underlying natural substance source
here, chitin, is a high molecular compound normally
characterized by molecular weights well above 1 million.
Chitin-based waste products, especially the shells or
crusts of crabs, crustacea and other organisms of marine
fauna, are abundantly available to modez~n food technology.
Various possible methods of exploitation are known;
reference may be made to the relevant literature cited
above. Exploitation of these waste products is also known
in the agrochemical sector in particular. In addition to
the literature already cited, reference may be made here to
US-PS 5,057,141 and the literature cited therein,
especially R. Rodriguez-Kabana et al. in "Plant and Soil",
100, 237 to 247 (1987), where it is described in particular
that chitin-containing materials mixed with other organic
CA 02348951 2001-04-26
nitrogen compounds, such as ammonium phosphate and urea,
develop a nematostatic and nematocidal activity towards
phytopathogenic nematode populations in soils and at the
same time, rather than being phytotoxic, serve to nourish
5 the plants. The teaching of US-PS 4,536,207 is along the
same lines, said patent describing the nematocidal action
of a chitin/protein complex compound obtained from a
demineralized water-insoluble chitin material and a water-
insoluble protein component.
The teaching according to the invention includes the use of
such water-insoluble chitins as active substance
component (a) or at least as part of this active substance
component.
By contrast, one important embodiment of the technical
teaching according to the invention is based on the object
of being able to bring about a marked increase in efficacy
precisely of nutrient mixtures (a) by using components
based on chitin or chitosan, at least some of which are
water-soluble. It is known that chitosan and chitosan
compounds are obtained by the deacetylation of chitin.
Although the primary product obtained, high molecular
chitosan - especially with molecular weights in the region
of 1 million or more - is as such insoluble or only poorly
soluble in water and aqueous alkali solutions, it is known
substantially to increase the solubility of this (these)
chitosan components) by simple means. Thus the chitosan-
based components dissolve in aqueous solutions of organic
and inorganic acids. It is also known that chitosan with a
degree of deacetylation of 50~ is water-soluble. The water
solubility can be increased by degrading the molecular
weights to the range of chitosan oligomers; finally, the
solubility can be adjusted over a wide pH range in water by
means of simple chemical reactions - especially by
carboxymethylation to O-CM-chitosan, N-CM-chitosan and/or
N/O-CM-chitosan. For details of this basic knowledge about
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11
chitosans, cf. e.g. the cited publication entitled
"Applicants of Chitin and Chitosan", M.F.A. Gossen (Ed.),
Technomic Publishing AG, 1997, chapter 1 entitled
"Applications and Properties of Chitosan", Q. Li et al.,
pages 3 to 29, particularly pages 8 and 9.
As already made clear, the chitosans (a) to be used
according to the invention can be oligomers and/or polymers
of practically any desired molecular weight. In the manner
already indicated, both low molecular oligomers and high
molecular polymers can be converted to water-soluble forms
which allow application to the soil and/or the aerial part
of the plants and the spreading of the chitosan in the soil
and especially into the region of the plants' roots.
Particularly suitable chitosan compounds in this connection
can be those which also have sufficient water solubility
especially in the neutral to weakly basic pH range and
which have been modified in a manner known per se - e.g. by
salification with inorganic and/or organic acids, by
lowering and regulation of the degree of polymerization or
oligomerization and/or by derivatization of the chitosans
with solubilizing groups, e.g. carboxymethyl groups in the
O- and/or N-position.
Although the published prior art also expressly describes
the use of such chitosans or chitosan compounds in the
agricultural sector, including the use of corresponding
aqueous chitosan formulations, the combination essential to
the invention, in terms of the multicomponent mixtures of
components (a) , (b) , (c) and preferably also (d) defined
according to the invention, coupled with the objective
according to the invention, on the one hand to increase
plant growth and on the other hand to protect the plants
from infestation by pathogens, particularly those
responsible for fungal, bacterial and/or viral diseases,
but also sucking pests, on the root - in this case e.g.
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12
nematodes - and/or on aerial parts of the plants, is not
disclosed in said published prior art.
The introduction of chitosan components (a) into the soil
regions to be treated and/or onto the aerial part of the
plants can be carried out at the same time as the
introduction of components (b), (c) and optionally (d),
and/or at a different time. In one important embodiment,
however, provision is made for sufficiently water-soluble
chitosans or chitosan compounds to be introduced into the
soil structure and/or applied to the aerial part of the
plants at least in part together with said other components
of the nutrient mixtures according to the invention.
If chitins and/or particularly chitosans are used in a
mixture with components (a), (b) and optionally (d), the
amounts used here are at least 0.05 wt.~ and especially at
least 0.1 to 1 wt.~, based in each case on the anhydrous
multicomponent mixture. The crucial point is that even
such small amounts of chitin-based or chitosan-based
components can substantially influence the course of the
vital processes in the soil and in the plant; in
particular, the growth of the healthy microbial flora and
hence of the plants is promoted and the growth of pests is
suppressed.
(b) "Ecoloqically compatible surfactant compounds of the
~W type (APG compounds)
The biodegradable surfactants of subclass (b) used
according to the invention are known to be compounds of
non-ionic character which are also preferably at least
predominantly based on natural substances and have
preferred HLB values in the range 10 to 18.
According to the invention, it is particularly preferred to
use, as component (b), at least partially, and especially
at least predominantly, alkyl(oligo)glucoside compounds
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13
whose alkyl radical is at least predominantly derived from
linear fatty alcohols. Compounds of this type - nowadays
also termed APG components or compounds - are surface-
active auxiliary substances with a wide range of
applications. Several factors are important for their
modern practical use on the industrial scale: It is known
that APG-based wetting agents can be completely based on
natural substances. They are the reaction products
obtained by reacting fatty alcohols with glucose,
l0 oligoglucoses or - in the case of simultaneous degradation
of the chain length - polyglycosides such as starch, said
reaction products having the general formula R-O-(G)x, in
which R is a primary, preferably linear and aliphatic
hydrocarbon radical having at least 6 C atoms, preferably
8
to 24 C atoms and particularly preferably 8 to 18 C atoms,
and G is a glycose unit having 5 or 6 C atoms, preferably
glucose. In the surfactant class in question, the degree
of oligomerization x - and hence the DP value - which
indicates the distribution of monoglycosides and
oligoglycosides, is conventionally between 1 and 10 and for
example is in the range from about 1.2 to 5, preferably in
the range from about 1.2 to 4 and particularly preferably
in the range from 1.2 to 2. Reference may be made to the
extensive specialized knowledge and literature on the
preparation and nature of APG compounds of the type in
question; cf., for example, the book by Hill et al.
entitled "Alkyl Polyglykoside" ("Alkylpolyglycosides"),
VCH-Verlagsgesellschaft mbH, Weinheim, 1997.
APG compounds as surface-active auxiliary substances in
aqueous formulations normally cause considerable foaming
when these aqueous formulations are discharged. The
teaching of German patent application DE 197 O1 127 cited
above illustrates the form in which low-foaming wetting
agents can be obtained precisely with such APG compounds.
Olefinically unsaturated alcohols and/or partial esters of
lower polyhydric alcohols with fatty acids can be used in
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14
particular as foam inhibitors/antifoams. These are
compounds which in principle can be assigned to
subclass (c) defined according to the invention, which will
therefore be described in detail below.
(c) "Organic compounds having lipophilic hydrocarbon
radicals with a fatty structure"
The concomitant use of this (these) component(s), in terms
of type and amount, is of decisive importance in the
preferred embodiment according to the invention. This
importance is normally based on several functions. As just
explained above, the class of nutrients discussed here
includes the category of foam inhibitors or antifoams which
are desirable or even necessary in connection with the use
of the surfactant components of class (b). In the
forefront, however, there is a quite different function
which is described in detail in earlier patent application
DE 197 48 884.6, already cited several times: The
components of this subclass are C sources for the growth of
the microbial flora in the rhizosphere and phyllosphere
regions.
An important characteristic of these additional
components (c) is the determining parameter that they are
both aerobically and anaerobically degradable by natural
processes. The C source which is essential according to
the invention for organotrophic growth is the lipophilic
hydrocarbon radicals with a fatty structure which are
present in this component, and hence the comparatively high
concentration of energy-providing C-H groupings. As
already explained above, these hydrocarbon radicals with a
fatty structure can be saturated and/or at least some of
them can be olefinically unsaturated. Further
considerations of the physicochemical nature of this
component, which will be described below, can be decisive
here.
CA 02348951 2001-04-26
Preferred components (c) are oil-soluble but biocompatible
organic compounds with fatty radicals of the indicated type
which have at least 6 C atoms and especially at least 8 C
atoms. It is preferred to use appropriate components based
5 on linear hydrocarbon radicals or HC compounds.
Appropriate components which are at least predominantly
based on natural substances are especially important.
Particularly important representatives of class (c)
10 referred to here are appropriate hydrocarbon compounds, at
least some of which are functionalized with oxygen as a
heteroatom. Typical examples of components of this type
are fatty alcohols and/or fatty acids or derivatives and/or
salts thereof. Suitable fatty alcohol or fatty acid
15 derivatives are their esters, ethers and/or amides. Of
particular importance within the framework of the invention
are fatty alcohols and the esters of fatty acids with
monohydric and/or polyhydric alcohols. Where polyhydric
alcohols are used, the term fatty acid esters includes both
full esters and partial esters. Which special components
are the preferred representatives in each specific
individual case is optionally determined by secondary
effects and hence by the presence of desirable or
undesirable synergistic effects within the entire system.
Appropriate statements made in German patent application P
19701127.6 will be discussed here solely by way of example:
Surfactant-based aqueous formulations and especially
corresponding aqueous APG-based wetting agents are normally
characterized by the high foaming capacity of these non-
ionic surface-active auxiliary substances based on APG.
This can prove extremely burdensome in the working area in
question according to the invention, which gives rise to
the additional object of remedying the situation by the
concomitant use of so-called foam inhibitors or antifoams.
This object is achieved by means of fatty alcohols, partial
esters of, in particular, lower polyhydric alcohols - e.g.
CA 02348951 2001-04-26
16
glycerol - and fatty acids, and especially mixtures
thereof. At the same time, however, they are the C sources
desired according to the invention for stimulating and
increasing microbial growth in the soil and thus are
optimum representatives of components (c) in terms of the
definition according to the invention.
The mixing of aqueous APG concentrates with antifoams/ foam
inhibitors based on alcohols and/or partial esters of fatty
acids and polyhydric alcohols, especially glycerol, can
lead to the formation of thickened gels which are no longer
capable of flowing, but the addition of limited amounts of
lower monohydric and/or polyhydric alcohols, e.g. limited
amounts of ethanol, to the nutrient concentrate which has
thickened to a gel then makes it possible to assure
flowability and pourability once again, even at around room
temperature.
In preferred embodiments, the nutrients or nutrient
mixtures to be used as mixing component (c) in a specific
individual case are thus determined not only by
considerations directed towards optimizing this component
as a carbon source for microbial growth. Secondary effects
can also be decisive, examples being low foaming capacity
of the aqueous multicomponent mixture, homogenization of
the multicomponent mixture containing lipophilic components
together with wetting agents of the O/W type in the aqueous
phase, and applicability in terms of dilution with more
water and subsequent distribution by pouring and/or
spraying. Patent application P 19701127.6 cited above
deals with these aspects in particular. To complete the
disclosure of the invention, the subject of said patent
application is also expressly incorporated here with the
subject of the disclosure of this invention.
It can be important, especially for trouble-free
introduction of the water-based mixtures of substances into
CA 02348951 2001-04-26
17
the soil substrate and transport of the carbon sources of
mixing component (c) in terms of the definition according
to the invention, to select components (c), at least some
of which have setting points equal to/below 25 to 30C and
especially equal to/below 10 to 15C, examples of suitable
components being olefinically unsaturated C12_z4 fatty
alcohols of natural origin and especially at least
predominantly Clsila fatty alcohols with a high proportion
of
olefinic double bonds and solidification ranges equal
to/below 20C, preferably equal to/below 10 to 15C.
Preferred multicomponent mixtures of this class (c) in
terms of the definition according to the invention are
mixtures of fatty alcohols and partial esters of saturated
fatty acids, and especially at least in part olefinically
unsaturated fatty acids, with polyhydric alcohols having 2
to 6 C atoms and especially 3 to 5 C atoms. Thus, in
particular, glycerol partial esters of fatty acids of
natural origin can be important mixing components for
mixing with appropriate fatty alcohols, preferred mixtures
of substances being approximately equal amounts of fatty
alcohol and fatty acid partial ester or corresponding
mixtures of substances containing a multiple amount of the
partial ester, based on the fatty alcohol. Suitable
mixtures of fatty alcohol to fatty acid partial glyceride
are for example in the range from about 1:1 to 1:10,
preferably from 1:1 to 1:5 and particularly preferably from
about 1:1 to 1:3 parts by weight. As indicated earlier,
however, such fatty acid partial esters can also be used
alone as components) (c). Here again, appropriate
representatives with setting points in the above-mentioned
ranges are preferred.
Another determining factor for the novel technical act
which is essential in terms of the invention - namely the
minimum amounts of C sources to be used in each case for
microbial growth within the framework of the total
multicomponent mixtures to be applied according to the
CA 02348951 2001-04-26
18
invention - will be discussed in detail at a later point.
Only the following will be made clear at this stage: As an
essential factor in one important embodiment, the teaching
according to the invention provides the proportioning of
component (c) to the amounts of P, and optionally other
macronutrients and micronutrients, introduced via mixing
component (d). The source (c) providing carbon for
microbial growth is used in minimum amounts such that -
based on the phosphorus P introduced via mixing
component (d) - the weight ratio C:P is at least in the
range from about 5 to 10:1 and is preferably at least about
to 25:1. However, depending on the nature of the soil
and especially on the type and amount of organically bound
carbon present in the soil region, embodiments may be
15 preferred in which substantially higher C:P ratios are
assured, important lower limiting values here being 40:1
and preferably in the region of at least 50:1. A very much
greater excess of the C source is normally also possible,
resulting in C:P weight ratios of up to 500:1 or even more
20 within the framework of the teaching according to the
invention. The stimulation and support of organotrophic
microbial growth in terms of the object according to the
invention are realized by optimizing the spreading of this
C source, readily accessible for microbial growth, in the
soil and by transporting it to the rhizosphere region.
With their lipophilic radicals of fatty character and their
aerobic as well as anaerobic degradability, the
nutrients (c) used according to the invention are
completely degradable to COZ, Hz0 and biomass. Consequently
it is certain that no inert or ecotoxicologically harmful
degradation products will accumulate in the soil as a
result of their use. Components (c) containing lipophilic
radicals migrate only slowly in the soil and they have a
tendency to attach themselves to lipophilic or oleophilic
surfaces and hence to root surfaces in particular. In
practical terms they are not washed out into the
CA 02348951 2001-04-26
19
groundwater, and they are not toxic, so they are safe to
use on this basis as well. The above-mentioned interaction
between the lipophilic radicals of mixing components (c)
used according to the invention and other constituents of
the substrate or of the multicomponent mixture added
according to the invention can be particularly important
when selecting suitable and optimized components for
class (d), which is discussed below.
(d) "P and/or N compounds at least some of which have
lipophilic radicals and if desired, carriers containing
other macronutrients and/or micronutrients for plant
growth"
Finally, in one preferred embodiment, the teaching of the
invention provides the introduction of nutrients or
nutrient mixtures selected from phosphorus-containing
and/or nitrogen-containing fertilizers into the substrate
to be treated and/or onto the aerial part of the plants,
especially the leaves. Components which carry both these
elements can be preferred representatives of this class of
substances. If desired, carriers containing other
macronutrients and/or micronutrients for plant growth can
be used in this connection - i.e. as partial constituents
of component (d). However, the following will be dealt
with first:
The introduction of this (these) nutrient components) (d)
can be effected simultaneously and in combination with the
introduction of the nutrients (c) and the ecologically
compatible wetting agents (b) used for this purpose, but it
is also possible to introduce these nutrient components (d)
at a different time or to combine said staggered
introduction with the simultaneous introduction of
components (a) , (b) , (c) and (d) .
One particularly important embodiment of the invention
provides the use of oil-soluble P and/or N compounds as
CA 02348951 2001-04-26
component (d), at least some of which has lipophilic
radicals. Particularly preferred representatives of these
auxiliary substances are thus the phospholipids described
in the publication DE 44 37 313 cited at the outset, and/or
5 derivatives thereof, as essential representatives of these
components (d). The subject of the disclosure of said DE
44 37 313 is also expressly incorporated here with the
subject of the disclosure within the framework of the
teaching according to the invention, so essential points of
10 view will be particularly emphasized below only in the form
of extracts. Said publication already emphasizes that the
action of the added phospholipids on the microbial soil
flora is expressed inter alia in the fact that organic
compounds and plant residues present in the soil are
15 degraded more rapidly, leading to an increase in soil
bacteria. In terms of the teaching according to the
invention, the flowable lipophilic components (c) are now
additionally made available as carbon sources for microbial
growth. Lipophilic molecular moieties of the
20 components (d) associate themselves with the lipophilic
radicals of the hydrocarbon type from the C sources (c) in
terms of the teaching according to the invention.
Unpredictably, a mobilization and strengthening precisely
of the microbial strains of the varied populations living
in the soil takes place, said populations leading - in
exchange with the plants' roots - to a lasting
strengthening of and increase in plant growth. It is clear
that, due to this, the acceleration of growth, at least in
its initial phases, acts independently of the organic
compounds, such as plant and root residues etc., present in
the soil. Nevertheless, in subsequent phases, the
composting process (mineralization) taking place in the
soil is also accelerated and dead plant material is
returned to the biological cycle more rapidly. Plant
nutrients fixed in the substrate become available to the
plants again. The aeration of the soil or substrate on
CA 02348951 2001-04-26
21
which the plants are growing is improved and the hydrologic
balance is stabilized.
Preferred components of nutrient class (d) are esters of
phosphoric acid with monohydric and/or polyhydric alcohols
which have lipophilic radicals in their molecular
structure. Corresponding phosphoric acid partial esters
are also particularly suitable here and are then normally
used in the form of their (partial) salts.
Suitable phosphoric acid esters in this sense are
accordingly partial esters of fatty alcohols which
introduce the required lipophilic moiety into the
phosphoric acid ester molecule via the hydrocarbon radical
of the fatty alcohol. Partial esters of phosphoric acid
with linear fatty alcohols which have preferably been
prepared, at least to a substantial extent, using C6_lo fatty
alcohols and/or their lower ethoxylates can be particularly
suitable for this purpose. In principle, however,
phosphoric acid esters of higher fatty alcohols having e.g.
12 to 24 C atoms are also suitable; correspondingly
olefinically unsaturated fatty alcohol radicals can also be
particularly important here.
Particularly preferred phosphoric acid esters of nutrient
subclass (d), however, are phospholipids and phospholipid
derivatives. As is known, these are amphiphilic substances
obtained from plant or animal cells. Preferred
phospholipids in terms of the teaching according to the
invention are corresponding compounds of vegetable origin
or phospholipid derivatives obtained therefrom.
Particularly preferred representatives of this class of
substances (a) are glycerophospholipids, which are
conventionally also called lecithin. Sphingophospholipids
are less preferred. Known substances which can be used
here are diacylphospholipids, phosphatidylcholines,
phosphatidylethanolamines, phosphatidylinositols,
CA 02348951 2001-04-26
22
phosphatidylserines, phosphatidylglycerols,
phosphatidylglycerol phosphates, diphosphatidylglycerol, N-
acylphosphatidylethanolamine and phosphatidic acid.
Monoacylphospholipids, lysophosphatidylcholines,
lysophosphatidylethanolamines, lysophosphatidylinositols,
lysophosphatidylserines, lysophosphatidylglycerols,
lysophosphatidylglycerophosphates,
lysodiphosphatidylglycerols, lyso-n-
acylphosphatidylethanolamines and lysophosphatidic acid are
preferred. Phosphatidylglycerides are industrially
available in large quantities and are marketed as vegetable
or animal lecithins and cephalins. These formulations are
obtained for example from oils such as maize oil,
cottonseed oil or soya oil. Components of subclass (a)
which are preferred according to the invention can be
enzymatically hydrolyzed glycerophospholipids
(enzymatically hydrolyzed lecithin), which have a more
hydrophilic character due to the cleavage of a fatty acid
ester, the only exceptions being products which have lost
their phosphoric acid residue as a result of the enzymatic
hydrolysis.
Preferred components (d) are lecithin, lecithin
hydrolyzates and/or chemically modified lecithins. These
compounds can also be used in a mixture with other N-
containing components, although the concomitant use of such
additional N components is expediently dispensed with for
application of the multicomponent mixture to the aerial
part of the plants, especially the leaves.
Numerical data for the proportions of nutrient components
(a) to (d), which are applied to the soil and/or to the
aerial part of the plants in a mixture with one another
and/or at different times, are first given below. The
numerical values which now follow relate to the particular
representatives of said nutrient class in percentages by
CA 02348951 2001-04-26
23
weight, based on an anhydrous or practically anhydrous
nutrient mixture.
The components (a), i.e. chitin and/or chitosans of
oligomeric and/or polymeric structure, are used in amounts
of at least 0.01 wt.% and preferably in amounts of at least
0.05 wt.%. Proportions of at least 0.1 to 1 wt.%, based in
each case on the practically anhydrous nutrient mixture,
are particularly preferred. The upper limit to the amount
of this constituent is determined by several factors, as
will be understood from the following considerations: If
soluble and especially water-soluble components (a) are
used, chitosans of oligomeric and/or polymeric structure
are the most appropriate choice. Here the molecular size
particularly of polymeric compounds - in conjunction with
the demand for flowable and pourable formulations - can
influence the upper limit to the amount of this
constituent. The situation is different if increased
solubility in water is assured by the above-mentioned
derivatization of the chitin and/or chitosan structure
and/or by the formation of sufficiently low oligomer types,
even at higher concentrations. The considerations dealt
with here also include especially the fact that the action
of components (a) against pathogens can be assured even at
very low use concentrations. Accordingly, upper limits to
the content of mixing components) (a) in the nutrient
mixture are e.g. 15 to 25 wt.%, but are preferably well
below these values, for example 5 to 10 wt.%.
The surfactants (b) from the class of the APG compounds of
the O/W type are conventionally used in amounts of about 5
to 45 wt.%, preferably in the range from about 10 to
wt.%, again based on the anhydrous nutrient mixture. In
the case of the concomitant use of organic compounds (c)
35 which have hydrocarbon radicals with a fatty structure and
are both aerobically and anaerobically degradable, the
amounts conventionally range up to about 40 wt.%,
CA 02348951 2001-04-26
24
preferably from 1 to 30 wt.~. Components (d) concomitantly
used in preferred embodiments - i.e. P and/or N compounds,
at least some of which have lipophilic radicals - can also
account for up to 40 wt.~s, preferably 3 to 30 wt.~, of the
multicomponent mixture.
When the chitin-based and/or chitosan-based multicomponent
mixtures are applied or introduced, different principles
can come into play which indirectly influence the amounts
of said multicomponent mixtures used in the operation
concerned. Thus, in a first embodiment, the simultaneous
and/or staggered introduction of the components or
component mixtures defined according to the invention may
be carried out only once over the particular plant growth
period in question. However, the possibility, provided
according to the invention, of working with water-soluble
and/or water-emulsifiable nutrient mixtures also opens the
way to introducing or applying the nutrients or nutrient
mixtures into the soil and/or to the aerial part of the
plants several times at shorter or longer intervals. Thus
it may be expedient repeatedly to apply comparatively small
amounts of the nutrients according to the invention at
intervals of at least 2 to 3 weeks, for example at
intervals of 1 to 2 months. This procedure makes it
possible to optimize the efficacy, even when only very low
concentrations of nutrients or nutrient mixtures are
introduced into the soil and/or onto the plant.
Accordingly, the preferred lower limits to the amounts of
nutrient mixtures according to the invention which are
applied or introduced are at least 0.1 to 0.2 g/m2,
preferably at least about 1 g/m2. The upper limits to the
amounts introduced can range from 40 to 60 g/m2, all these
numerical values again being based on the practically
anhydrous components introduced in a mixture or at
different times. Corresponding amounts ranging from about
0.5 to 10 g/m~, especially from about 1 to 5 g/m2, are
suitable precisely for the above-mentioned possibility of
CA 02348951 2001-04-26
the multiple introduction of comparatively low
concentrations of nutrients or nutrient mixtures.
In one important embodiment, the teaching according to the
5 invention provides the use of the above-described nutrients
and nutrient mixtures in addition to the currently
conventional introduction of plant protection agents in
plant cultivation, possible examples being conventional
auxiliary substances for combating fungal, bacterial and/or
10 viral diseases, but also sucking pests, on the root and/or
aerial parts of the plants. Specific reference may be made
here to the specialized knowledge of the auxiliary
substances used according to modern practice, for example
to the agriculture textbook by K.-U. Heyland entitled
15 "Allgemeiner Pflanzenbau" ("General Plant Production"),
Verlag Eugen Ulmer, Stuttgart, 1996, especially
subchapter 8 thereof entitled "Schaderreger and
Pflanzenschutz" ("Pathogens and Plant Protection"), loc.
cit., pages 251 to 356, and the publication by H. Burner
20 entitled "Pflanzenkrankheiten and Pflanzenschutz" ("Plant
Diseases and Plant Protection"), 5th edition, Verlag Eugen
Ulmer, Stuttgart, 1983, pages 136 to 154, and the
literature cited therein.
25 If such a combination of the teaching according to the
invention with conventional auxiliary substances is used
against said pathogens, the amount of these conventional
auxiliary substances used can be substantially reduced
without fear of serious activity losses. This procedure
allows savings of at least 30~, preferably of at least 50
to 75~, on the active substances of the prior art which
conventionally originate from synthetic chemistry, without
fear of losing growth and/or yield. However, as already
stated, this combined use of the teaching according to the
invention with the relevant previous technical knowledge
represents only one possible embodiment in terms of the
teaching according to the invention. It is preferred
CA 02348951 2001-04-26
26
according to the invention to dispense completely or
practically completely with auxiliary substances of the
type extensively used in modern practice and described in
the prior art.
Finally, in another embodiment, the teaching according to
the invention includes a modification of the illustrated
technical teaching in such a way that the concomitant use
of the chitin-based and/or chitosan-based components (a) of
oligomeric and/or polymeric structure is dispensed with,
but now the concomitant use of component (d) - P and/or N
compounds, at least some of which have lipophilic radicals
is obligatorily associated with the use of APG compounds
of the O/W type - compounds (b) - and with components (c),
i.e. organic compounds which have lipophilic hydrocarbon
radicals with a fatty structure and are both aerobically
and anaerobically degradable.
The last-mentioned embodiment of the technical teaching
takes up the disclosure of earlier German patent
application DE 198 30 889 (H 3571) in the name of the
Applicant, which provides the use of aqueous formulations
of
- fatty alcohols and/or partial esters of fatty acids with
lower polyhydric alcohols, mixed with
- ecologically compatible surfactant compounds from the
class of the alkyl(poly)glycosides of the O/W type (APG
compounds)
as a nutrient mixture with a plant strengthening and/or
plant restoring action against infestation thereof by
phytopathogenic fungi and/or soil-borne pests. The
disclosure of the above-mentioned earlier patent
application is also expressly incorporated here with the
subject of the disclosure of this invention, especially in
connection with the last-mentioned embodiment. The
CA 02348951 2001-04-26
27
decisive modification which is now disclosed involves the
concomitant use of components (d) together with the APG
compounds and particularly fatty alcohols and/or partial
esters of fatty acids with lower polyhydric alcohols, but
also with other oxygen-functionalized components having
fatty radicals, and compounds described as component (c) in
terms of this invention. The amounts indicated here, both
for the individual components in relation to one another in
the multicomponent mixtures, and for the application of the
multicomponent mixtures to the soil and/or the aerial part
of the plants - as previously given for the mixtures of
substances (a) to (d) described according to the invention
still apply.
1
CA 02348951 2001-04-26
28
Examples
The following formulations I and II describe aqueous,
flowable and water-dilutable concentrates of chitosan-
containing nutrient components in terms of the invention,
which can be diluted with more water and can easily be used
in this form for plant protection in terms of the teaching
according to the invention.
The components denoted by trade names in these Tables for I
and II are as follows:
Glucopon 215 CS UP APG-based O/W wetting agent
HD Ocenol or HD Ocenol 80/85 C16-18 fatty alcohol, iodine
number 80-85
Edenor GMO glycerol monooleate
Lipotin NE enzymatically hydrolyzed
soya lecithin
The aqueous chitosan solution used was a water-soluble
chitosan polymer prepared by stirring 1 g of chitosan
polymer with 5 ml of 1 molar HC1 and 100 ml of water at
room temperature until the chitosan had dissolved.
Formulation I
Raw materia Inltia weig t Wt.~
Glucopon 215 CS UP 40 g 40
HD Ocenol 5 g 5
3 H20 15 g 15
0
1~ chitosan
solution, acidic 20 g 20
Lipotin NE 20 g 20
100 g 100.0
CA 02348951 2001-04-26
29
The aqueous active substance mixture indicated here
contains 65 wt.% of nutrients in terms of the definition
according to the invention in 35 wt.~ of water. The
chitosan content of the active substance mixture is
0.31 wt.~, based on the anhydrous nutrient mixture.
In laboratory experiments, use quantities of the
multicomponent mixture which correspond to an application
quantity of 1 g/m2 when discharged onto the soil show a
marked inhibition of fungal growth in appropriately
infested nutrient substrates.
The same applies to tests on a nutrient mixture in terms of
the invention which is characterized by formulation II
below.
Formulation II
Raw materia Initia weig t
Glucopon 215 CS UP 340 g
HD Ocenol 80/85 56 g
Edenor GMO 110 g
Ethanol 120 g
H20 150 g
1~ c itosan
solution, acidic 120 g
896 g
The nutrient mixture shown in this Table contains 70 wt.~
of active substances mixed with 30 wt.~ of water. The
chitosan content of the anhydrous nutrient mixture is
0.19 wt.~.
The formulations in Table I and Table II can be diluted
with water in practically all proportions. Laboratory
tests on formulation II again show a marked reduction in
CA 02348951 2001-04-26
fungal growth in appropriately infested experimental soils
when the product is used in an amount of 1 g/mz.
t
1
