CA2348951A1 - Use of useful substances to promote the growth and health of plants - Google Patents
Use of useful substances to promote the growth and health of plants Download PDFInfo
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- CA2348951A1 CA2348951A1 CA002348951A CA2348951A CA2348951A1 CA 2348951 A1 CA2348951 A1 CA 2348951A1 CA 002348951 A CA002348951 A CA 002348951A CA 2348951 A CA2348951 A CA 2348951A CA 2348951 A1 CA2348951 A1 CA 2348951A1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P21/00—Plant growth regulators
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G7/00—Botany in general
- A01G7/06—Treatment of growing trees or plants, e.g. for preventing decay of wood, for tingeing flowers or wood, for prolonging the life of plants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
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- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Ecology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Botany (AREA)
- Forests & Forestry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Cultivation Of Plants (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Fertilizers (AREA)
- Pretreatment Of Seeds And Plants (AREA)
Abstract
The invention relates to the use of multi-ingredient mixtures of useful materials that are at least predominantly of an organic nature in the cultivation and care of useful and ornamental plants by activating the rhizosphere and/or phyllosphere and promoting plant growth and improving the health of said plants with respect to damage causing agents in the form of fungal diseases, bacterioses and/or viroses in addition to parasites that attack roots and/or parts of the plant above the ground. Said mixtures contain: (a) chitin and/or chitosan with an oligomeric and/or polymeric structure in combination with and with simultaneous or delayed application of (b) ecologically compatible surfactant compounds from the following class:
alkyl(poly) glycosides of the O/W variety (APG compounds) and (c) liphophilic saturated and olefinically unsaturated hydrocarbon radicalsith a fatty structure and aerobically and anaerobically degradable organic compounds.
Preferably, other ingredients that are used are characterized by compounds of P and/or Nith at least partially lipophilic radicals. If desired, said compounds can be used in conjunction with other macronutrients and micronutrients to promote plant growth in the root area and/or parts of the plant above the ground.
alkyl(poly) glycosides of the O/W variety (APG compounds) and (c) liphophilic saturated and olefinically unsaturated hydrocarbon radicalsith a fatty structure and aerobically and anaerobically degradable organic compounds.
Preferably, other ingredients that are used are characterized by compounds of P and/or Nith at least partially lipophilic radicals. If desired, said compounds can be used in conjunction with other macronutrients and micronutrients to promote plant growth in the root area and/or parts of the plant above the ground.
Description
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
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
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 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.
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, 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 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 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.
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 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 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.
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 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 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 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.
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.
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 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 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 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 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 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, 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 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.%, 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 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 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 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.
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 1~ chitosan solution, acidic 20 g 20 Lipotin NE 20 g 20 100 g 100.0 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 fungal growth in appropriately infested experimental soils when the product is used in an amount of 1 g/mz.
t
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 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.
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, 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 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 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.
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 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 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.
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 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 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 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.
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.
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 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 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 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 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 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, 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 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.%, 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 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 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 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.
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 1~ chitosan solution, acidic 20 g 20 Lipotin NE 20 g 20 100 g 100.0 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 fungal growth in appropriately infested experimental soils when the product is used in an amount of 1 g/mz.
t
Claims (15)
1. 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, containing (a) chitin and/or chitosan of oligomeric and/or polymeric structure, applied, simultaneously and/or at different times, in combination with (b) ecologically compatible surfactant compounds from the class of the alkyl(poly)glycosides of the O/W
type (APG compounds) and (c) organic compounds which have lipophilic, saturated and/or olefinically unsaturated hydrocarbon radicals with a fatty structure and are both aerobically and anaerobically degradable.
type (APG compounds) and (c) organic compounds which have lipophilic, saturated and/or olefinically unsaturated hydrocarbon radicals with a fatty structure and are both aerobically and anaerobically degradable.
2. Use according to Claim 1, characterized in that - as component(s) (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 are additionally introduced into the root region and/or applied to the aerial part of the plants.
3. Use according to Claims 1 and 2, characterized in that oil-soluble but biocompatible organic compounds with aliphatic and/or olefinically unsaturated, preferably at least predominantly linear hydrocarbon radicals which have at least 6 C atoms and especially at least 8 C atoms are used as component (c).
4. Use according to Claims 1 to 3, characterized in that components (c) are used, at least some of which are functionalized with oxygen as a heteroatom, it being preferred to use fatty alcohols and/or fatty acids or derivatives thereof, such as their esters or partial esters, ethers and/or amides.
5. Use according to Claims 1 to 4, characterized in that components (c) are at least predominantly based on natural substances.
6. Use according to Claims 1 to 5, characterized in that at least some of components (c) have setting points equal to/below 25 to 30°C and especially equal to/below 10 to 15°C.
7. Use according to Claims 1 to 6, characterized in that, as components (d), lecithin, lecithin hydrolyzates and/or chemically modified lecithins are used which can also be mixed 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.
components is expediently dispensed with for application of the multicomponent mixture to the aerial part of the plants, especially the leaves.
8. Use according to Claims 1 to 7, characterized in that chitosans or chitosan compounds, at least some of which are water-soluble, are used as component (a) and are preferably introduced into the cultivated land or applied to the aerial part of the plants in the form of aqueous formulations.
9. Use according to Claims 1 to 8, characterized in that chitosans of oligomeric and/or polymeric structure are used which have been obtained by at least extensive deacetylation of chitin and, if desired, reduction of the average molecular weight by chain cleavage of the aminosaccharide polymers.
10. Use according to Claims 1 to 9, characterized in that chitosan compounds with improved water solubility preferably also in the neutral to weakly basic pH
range - are used, it being possible for the water solubility to be assured 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.
range - are used, it being possible for the water solubility to be assured 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.
11. Use according to Claims 1 to 10, characterized in that, as component (b), APG compounds are used whose alkyl radical is at least predominantly derived from linear fatty alcohols which are preferably based on natural substances, and also the HLB values of these surfactant components are preferably in the range 10 to 18.
12. Use according to Claims 1 to 11, characterized in that the APG compounds used as component (b) consist of glucose and fatty alcohols based on natural substances with at least 6 C atoms, preferably 8 to 24 C atoms, and have DP values in the range 1.2 to 5.
13. Use according to Claims 1 to 12, characterized in that the multicomponent mixtures are used in the form of low-foaming aqueous formulations which - as at least some of components (c) - contain olefinically unsaturated C12-24 fatty alcohols of natural origin, especially at least predominantly C16-18 fatty alcohols with a high proportion of olefinic double bonds and solidification ranges equal to/below 20°C, preferably equal to/below 10 to 15°C, and/or fatty acid partial esters such as glycerol monooleate, it also being possible to use mixtures of such components (c).
14. Use according to Claims 1 to 13, characterized in that the chitin-based and/or chitosan-based active substance components (a) in the nutrient mixture are present or used in amounts of at least 0.05 wt.%, preferably in amounts of at least 0.1 to 1 wt.%, based in each case on the anhydrous nutrient mixtures.
15. Use according to Claims 1 to 14, characterized in that the chitin-based and/or chitosan-based multicomponent mixtures are distributed in amounts of at least 0.2 g/m2, preferably in amounts of 1 to 60 g/m2 and particularly preferably in amounts of 10 to 40 g/m2, based on the anhydrous mixture.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19849253.7 | 1998-10-26 | ||
DE19849253A DE19849253A1 (en) | 1998-10-26 | 1998-10-26 | Natural material based preparation for strengthening plants and improving resistance to fungi and soil pests contain alkyl (poly)glycosides plus fatty alcohols and/or polyol partial esters |
PCT/EP1999/007860 WO2000024255A1 (en) | 1998-10-26 | 1999-10-16 | Use of useful substances to promote the growth and health of plants |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2348951A1 true CA2348951A1 (en) | 2000-05-04 |
Family
ID=7885635
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002348951A Abandoned CA2348951A1 (en) | 1998-10-26 | 1999-10-16 | Use of useful substances to promote the growth and health of plants |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP1124420A1 (en) |
JP (1) | JP2002528396A (en) |
KR (1) | KR20010080331A (en) |
CN (1) | CN1328418A (en) |
AR (1) | AR020940A1 (en) |
AU (1) | AU1039900A (en) |
BR (1) | BR9914802A (en) |
CA (1) | CA2348951A1 (en) |
CO (1) | CO5231141A1 (en) |
DE (1) | DE19849253A1 (en) |
HK (1) | HK1039438A1 (en) |
ID (1) | ID29588A (en) |
WO (1) | WO2000024255A1 (en) |
ZA (1) | ZA200103385B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19961937A1 (en) | 1999-12-22 | 2001-06-28 | Cognis Deutschland Gmbh | Plant growth promoter comprises multi-component mixture as solid, anhydrous aggregate |
JP4879424B2 (en) * | 2001-09-25 | 2012-02-22 | 花王株式会社 | Plant vitality composition |
JP5446807B2 (en) * | 2008-12-16 | 2014-03-19 | 王子ホールディングス株式会社 | Liquid fertilizer composition |
FR3023452B1 (en) | 2014-07-11 | 2016-07-08 | Prp Holding | USE OF AN ORGANO-MINERAL COMPOSITION TO INCREASE THE ASSIMILATION OF NUTRIENT ELEMENTS OF SOIL BY THE PLANT |
KR102343292B1 (en) * | 2019-10-21 | 2021-12-27 | 한국생명공학연구원 | Composition comprising lyso-phosphatidylethanolamine 18:2 to alleviate symptoms of plant virus diseases and uses thereof |
CN114208652A (en) * | 2021-12-13 | 2022-03-22 | 水生藻安生物科技(武汉)有限公司 | Planting culture device for aquatic plant cultivation, preparation method and application |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5673002A (en) * | 1979-11-16 | 1981-06-17 | Kuraray Co Ltd | Fungicide of terpene alcohol for agriculture and horticulture |
DE3545908A1 (en) * | 1985-12-23 | 1987-06-25 | Henkel Kgaa | USE OF LONG-CHAIN ETHERS IN PLANT PROTECTION PRODUCTS |
US5385750A (en) * | 1992-05-14 | 1995-01-31 | Henkel Corporation | Alkyl glycoside compositions with improved wetting properties |
GB2279359A (en) * | 1993-06-24 | 1995-01-04 | Unilever Plc | Fibre treatment materials and compositions containing them |
IT1275167B (en) * | 1995-02-23 | 1997-07-30 | Isagro Spa | ADJUVANTS FOR SYSTEMIC FUNGICIDES FUNGICIDAL COMPOSITIONS THAT CONTAIN THEM AND THEIR USE |
WO1996028022A2 (en) * | 1995-03-08 | 1996-09-19 | Mycogen Corporation | Fatty acid based compositions and methods for the control of plant infections and pests |
AU7279496A (en) * | 1995-10-13 | 1997-05-07 | Novo Nordisk A/S | Fungicidal carbohydrate preparations |
US5674897A (en) * | 1995-10-20 | 1997-10-07 | Mycogen Corporation | Materials and methods for controlling nematodes |
US5770543A (en) * | 1996-09-06 | 1998-06-23 | Henkel Corporation | Agricultural compositions comprising alkyl polyglycosides and fatty acids |
DE19701127A1 (en) * | 1997-01-15 | 1998-07-16 | Henkel Kgaa | Low-foaming surfactant concentrates for use in the promotion of plant growth |
IL122967A0 (en) * | 1997-01-23 | 1998-08-16 | Dcv Inc | Method for treating cotyledonous plants |
DE19719856A1 (en) * | 1997-05-12 | 1998-11-19 | Henkel Kgaa | Skin care products |
DE19748884A1 (en) * | 1997-11-06 | 1999-05-20 | Henkel Kgaa | Flowable multi-component mixtures to promote the growth of the soil microorganism flora and their application |
-
1998
- 1998-10-26 DE DE19849253A patent/DE19849253A1/en not_active Withdrawn
-
1999
- 1999-10-16 CN CN99812613A patent/CN1328418A/en active Pending
- 1999-10-16 BR BR9914802-1A patent/BR9914802A/en not_active Application Discontinuation
- 1999-10-16 EP EP99953862A patent/EP1124420A1/en not_active Withdrawn
- 1999-10-16 AU AU10399/00A patent/AU1039900A/en not_active Abandoned
- 1999-10-16 WO PCT/EP1999/007860 patent/WO2000024255A1/en not_active Application Discontinuation
- 1999-10-16 KR KR1020017005195A patent/KR20010080331A/en not_active Application Discontinuation
- 1999-10-16 ID IDW00200101069A patent/ID29588A/en unknown
- 1999-10-16 JP JP2000577883A patent/JP2002528396A/en active Pending
- 1999-10-16 CA CA002348951A patent/CA2348951A1/en not_active Abandoned
- 1999-10-21 CO CO99066456A patent/CO5231141A1/en not_active Application Discontinuation
- 1999-10-22 AR ARP990105344A patent/AR020940A1/en unknown
-
2001
- 2001-04-25 ZA ZA200103385A patent/ZA200103385B/en unknown
-
2002
- 2002-02-04 HK HK02100831.1A patent/HK1039438A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
CN1328418A (en) | 2001-12-26 |
CO5231141A1 (en) | 2002-12-27 |
HK1039438A1 (en) | 2002-04-26 |
AU1039900A (en) | 2000-05-15 |
WO2000024255A1 (en) | 2000-05-04 |
DE19849253A1 (en) | 2000-04-27 |
ID29588A (en) | 2001-09-06 |
AR020940A1 (en) | 2002-06-05 |
EP1124420A1 (en) | 2001-08-22 |
BR9914802A (en) | 2001-07-10 |
KR20010080331A (en) | 2001-08-22 |
JP2002528396A (en) | 2002-09-03 |
ZA200103385B (en) | 2002-07-25 |
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Legal Events
Date | Code | Title | Description |
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FZDE | Discontinued |