CA2029877A1 - Phytosanitary agent and its use - Google Patents
Phytosanitary agent and its useInfo
- Publication number
- CA2029877A1 CA2029877A1 CA 2029877 CA2029877A CA2029877A1 CA 2029877 A1 CA2029877 A1 CA 2029877A1 CA 2029877 CA2029877 CA 2029877 CA 2029877 A CA2029877 A CA 2029877A CA 2029877 A1 CA2029877 A1 CA 2029877A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- agent according
- amount
- agent
- phytosanitary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
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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
- A01N3/00—Preservation of plants or parts thereof, e.g. inhibiting evaporation, improvement of the appearance of leaves or protection against physical influences such as UV radiation using chemical compositions; Grafting wax
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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
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/20—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation using specific microorganisms or substances, e.g. enzymes, for activating or stimulating the treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Microbiology (AREA)
- Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Tropical Medicine & Parasitology (AREA)
- Biochemistry (AREA)
- Mycology (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Fertilizers (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Abstract A phytosanitary agent which contains I) at least two amino acids and/or natural carboxylic acids or their derivatives or salts, II) purines and/or pyrimidines or their derivatives and III) vitamins or derivatives or precursors thereof, there being about 0.001 to 1 part by weight of a single compound of group II) and about 0.001 to 1 part by weight of a single compound of group III) for about 0.1 to 10 parts by weight of a single compound of group I), is described. This agent opens up the widest variety of possible uses. It is preferably used for preventing and controlling plant diseases of biotic origin and for increasing and ensuring the yield of crop plants. It displays its activity especially when used together with extracts from fermentation products (for example com-posts), whose intrinsic action it enhances. Within the scope of the possible uses mentioned above, the desired effects are achieved even when only one amino acid is present in the composition described.
Description
~ 2~329~77 - ` ~ -la-..
BTC Biotechnik Munich International Gmb~ Mar. 27, 1990 Our file: Pat 911/1-9OCh-PCT
Title: Phytosanitary aqent and its use Field of the invention and prior_art Composts of microorganic material ara distin-guished by a particularly wide variety of microorganisms, their metabolic products and other organic and inorgan.ic S compounds. Besides their importance as organic fertili-zers, they have long been a~tributed with possible beneficial effects on plant health. Thus, extracts from bark composts are said to have a fungicidal and fungi-static action again~t various Phytophthora species native to the soil. Com2ost extracts are, in general, fermenta-tion products from plant~ and plant residues, animal xesidues, marine brown algae or mixtures thereof.
It has already been disclosed that aqueous extracts or pressed ~uices from fermented organic sub-stances display, when they are applied to the green partsof plants, ~uch as lea, stem, fruits of plants or seeds, a phytosanitary action. Effects of this type have been reported by H.C. Weltzien et al. in ~Nachrichtenblatt deutscher Pflanzenschutz" (Braunschweig), 39, 1987, pp.
25 et seq. The results of the experiments carried out therein demonstrate the beneficial actions, which have been widely assumed, of composts and compost extracts on plant health. It was ~hown that the extracts induce resistance mechanisms in the treated plants and/or ha~e a direct effect on the pathogens.
Furthermore, there are known to be supplementary substances which many microorganisms require f~r their nutrition in addition to the minerals and the sources of carbon, of nitrogen and of ener~y. They belong to the basic constituent of thP cell, and some microorganisms cannot synthesize them from simple building blocks. The~e include amino acids, carboxylic acids, purine , p~rimi-dines, carbohydrates and vitamins. The supplementary substances differ distinctly from nutrients in terms of . . . -~. ''.''"
` 2~29877
BTC Biotechnik Munich International Gmb~ Mar. 27, 1990 Our file: Pat 911/1-9OCh-PCT
Title: Phytosanitary aqent and its use Field of the invention and prior_art Composts of microorganic material ara distin-guished by a particularly wide variety of microorganisms, their metabolic products and other organic and inorgan.ic S compounds. Besides their importance as organic fertili-zers, they have long been a~tributed with possible beneficial effects on plant health. Thus, extracts from bark composts are said to have a fungicidal and fungi-static action again~t various Phytophthora species native to the soil. Com2ost extracts are, in general, fermenta-tion products from plant~ and plant residues, animal xesidues, marine brown algae or mixtures thereof.
It has already been disclosed that aqueous extracts or pressed ~uices from fermented organic sub-stances display, when they are applied to the green partsof plants, ~uch as lea, stem, fruits of plants or seeds, a phytosanitary action. Effects of this type have been reported by H.C. Weltzien et al. in ~Nachrichtenblatt deutscher Pflanzenschutz" (Braunschweig), 39, 1987, pp.
25 et seq. The results of the experiments carried out therein demonstrate the beneficial actions, which have been widely assumed, of composts and compost extracts on plant health. It was ~hown that the extracts induce resistance mechanisms in the treated plants and/or ha~e a direct effect on the pathogens.
Furthermore, there are known to be supplementary substances which many microorganisms require f~r their nutrition in addition to the minerals and the sources of carbon, of nitrogen and of ener~y. They belong to the basic constituent of thP cell, and some microorganisms cannot synthesize them from simple building blocks. The~e include amino acids, carboxylic acids, purine , p~rimi-dines, carbohydrates and vitamins. The supplementary substances differ distinctly from nutrients in terms of . . . -~. ''.''"
` 2~29877
- 2 -their function and concentration.
The po~sibilities, which have been identified above, of diminishing or elLminating or preventing, by composts and compost extracts, attack by diseases on plants and plant parts are not as yet satisfactory.
Various ~ubstance mixl:ures attributed with a phytosanitary action ha~e been di closed. Thus, SU-14 46 155 A describes an agent which contains an amino acid, a purine and a vitamin. It is used as additivo to the nutrient ~olution of tissue cultures in order to achieve regeneration of the plant organ~ and ~trengthen-ing of the young plants. It i~ not intended for plant protection and for application to above-ground plant parts. EP-A-0,253,714 deals with 2-componant mixture~
which have fungicidal activity and have a pyrLmidine derivative and alanine or a derivative thereof.
EP-A-0,044,224 is concerned with the combination of chlorocholine chloride and the "metabolic additivesl' ~including vitamins, amino acids, purines, pyrimidines, carboxylic acids). Neither chlorocholine chloride nor the metabolic additives alone are said to have a fungicidal action. DD-A-63,669 relates to a systemic fungicide which contains a combination of one part of a glycine deri~a-tive and 0.02 to 2 parts of an NB-substituted adenine.
2S Only one purine (adenine) and one amino acid (glycine) is cited. WO 79/008 38 relates to chemicals which can be used in agriculture, such as fungicides, herbicides and plant-growth regulators, and one or more of the following additives are cited: carbohydrates, organic acids (especially fatty acids), vitamins and coenzymes, purine and pyrimidine nucleosides and nucleotides, naturally occurring fats and oils, certain amino acids and, where these chemicals which can be used in agriculture are not themselves plant-growth regulators, such regulators.
DE-A-26 25 398 deals with an agent and a method for stimulating the germination of potatoes, the latter necessarily containing an amino acid in the form of cysteine and a purine in the form of kinetin.
2~29~77 ` 3 Summary of the invention:
The agents identified above give no clear teach-ing of how a phytosanitary agent might very generally be designed in order to open up the most wide ranging possible uses. This also applies to the possibilities, which ha~e been mentioned, of rleducing or eliminating by composts and compost e~tracts, attack .. .. . . . . ... .
by diseases on plants and plant: parts. Hence the ob~ect of the invention was to provide a remedy for this.
This is achieved according to the invention by a phytosanitary agent which is characterized in that it C contains I) natural carboxylic acids or their salts and/or at least two amino acids or their salts, II) purines and/or their derivatives, especially nucleo-~ides, nucleotides and salts thereof and/or pyrimidine~
an~/or their derivatives, especially nucleoside-~, nucleo-tides and salts thereof, and the salts of the purines and pyrimidines and III) vitamins or derivatives or precursors thereof, there being about 0.001 to 1 part by weight of a single compound of group II) and about 0.001 to 1 part by weight of a single compound of group III) for about 0.1 to 10 part~ by weight of a single compound of group I).
Accordingly, the central concept of the phyto-sanitary agent according to the invention is to employ at least two amino acids or their salts in the substance composition described qualitatively and quantitatively above. In this connection, it is preferable to use three, four or even more amino acids or their salts. This opens up the widest possible use of this agent with the desired phytosanitary effect. It has emerged that for certain uses it i~ possible to dispense with the requirement for at least two or more amino acid~, and this will be dealt with hereinafter.
The effects associated with the incorporation of at least two amino acids in the phytosanitary agent according to the inYention can b~ explained technologi-cally as follows:
2~2~77 The phytosanitary action of agents of this type on the surface of leaves is based on encouragement of non-pathogenic microorganism~. The encouraged microorganisms are able to suppress the pathogenic fungi or bacteria S either indirectly by competition for food or directly by antagonism and thus to elicit the phytosanitary effect.
Examples of possible microorganisms with a beneficial action known in this connect;ion are Pseudomonas and Bacillus species and various yeasts. Countless other microorganisms may be concerned. These microorganisms have different nutrient requirements, also with -regard to the various amino acids. Their nutrient xequirements are accordingly met by providing various amino acids, especially two or more, in the particular agent. Determination of the nutrient needs of all the microorganisms with a beneficial action on the surface of leaves (phyllosphere), taking account of the requirements of pathogenic microorganisms, is possible not only for a plant/pathogen systemD The determined nutrient combina-tion i~ then a compromise between the greatest possibleencouragement of the antagonists and of the competitors and the substantial avoidance o~ encouragement of patho-genic fungi and bacteria. The number of proteinogenous amino acids (21) is considerably larger than the number 25 of particularly suitable vitamins (11), purines (4), pyrimidines (3) or carboxylic acids (11) if the pre-cursors and derivatives are let out of account. Thus t the probability that two or more amino acids are advan-tageous i-~ considerably greater than in the case of vitamins, purines, pyrimidines or carboxylic acids. It is furthermore known that phyllosphere microorganisms live in a close biotic community with the plant. However, there is massive excretion of amino acids by th~ plants -both via roots and via leaves. The amino acids play an35 important part in the evolutionary adaptation of micro-organisms to the specific conditions of the surface of leaves. This might have led to the par~icular amino acid needs of phyllosphere microorganisms.
The invention particularly relates to the use of . ~,, 2~29~77 the phytosanitary agent according to the invention, which i~ described above, for the t:reatment of above-ground plant parts and harvested proclucts, especially for the prevention and control of plant dis~ases of biotic origin with a view to increasing ancl ensuring yields. It is particularly advantageous in this area of use, as desc-ribed hereinafter, to employ, mixed with the agent according to the invention, fermentation products from plants and plant residues, marine brown algae, animal residues or mixtures thereof, enriched with micro-organisms, especially bacteria, yeasts, fungi and single-C cell algae. Within the scope of these advantageous - possible use~ twith and without fermentation products~, `
the value of the invention is particularly evident when the particular agent is used to control Phytophthora infestans, Botrytis cinerea, Plasmopara viticola, Erysiphe graminis, Uncinula necator, Tilletia sp. and Pseudopeziza tracheiphila.
If fermentation products are employed mixed with the phytosanitary agent according to the invention, the mixing ratio does not normally play a crucial part in this connection. As a rough guideline, a mixing ratio, based on dry matter, of about l part by weight of phyto-~anitary agent according to the invention to 100 to lO,000, especially 300 to 3000, parts by weight of fermentation product, based on dry matter, might be mentioned. -~ ` -It ha~ emerged, in the advantageous areas of use, mentioned above, for the treatment of above-ground plant parts and harvested products, especially for the preven-tion and control of plant diseases of biotic origin with a view to increasing and ensuring yields, and with inclusion of the fermentation products and the like, especially for controlling Phytophthora infestans, Botrytis cinexea, Plasmopara viticola, Erysiphe graminis, Uncinula necator, Tilletia sp. and Pseudopeziza tracheiphila, that satisfactory effects can be achieved in this connection even if the requirement, described above, to employ in the phytosanitary agent according to :- .,: ~ ', '' :- ~ 2029~77 the invention at least two or more amino acids is dispensed with and the composition according to the invention contains only one amino acid or its salt.
Accordingly, the invention is also intended to relate to S the use of a phytosanitary agent of the composition, described above, of components I), II) and III), in which cnly one amino acid or its ~alt is employed.
On the basis of the outline conditions identified above, the procedure for putting the present invention into practice is preferably as follows~
If the phytosanitary agent according to the invention contains a single compound of group I), its amount is preset and on its ba~is, taking account of the outline conditions identified above, the particular amount of the individual compounds of group II) and III) is determined. If group I) embraces several compounds, it is advisable to use as a basis that individual compound which occupies a central position in terms of weight within group I). In the case where two or more compounds of group I) are present in the phytosanitary agent according to the invention, it i~ expedient to use as a ~asi~ the mean thereof. Each individual compound o groups II) and III) is related, in the identified range of amounts, with the amount of group I) used as a basis.
C 25 This means that, for example, there is from group II) 0.001 to 1 part by weight of a single compound A), 0.001 to 1 part by weight of a single compound B) etc. for 0.1 to 10 parts by weight of the preset amount of a compound of group I).
It is preferable to use about 0.1 to 5 parts by weight, especially about 0.5 to 5 parts by weight, of a single compound of group I) as a basis. The following amino acids are preferred: L-aspartic acid, L-glutamic acid, L-histidine, L-arginine, L-alanine, L-serine, D-and/or L-tryptophan, L-tyrosine, D- and/or L-phenyl-alanine, L-asparagine, L-ly~ine, L-methionine, L-threon-ine, D- and/or L-glutamine, L-proline, L-hydroxyproline, D- and/or L-~aline, L-leucine, L-glycine, L-cystine and L-isoleucine. When carboxylic acids are included, it is :,~-.,.,, preferable for the agent according to the invention to contain at least one of the following natural carboxylic acids or their salts: pyruvic acid, lactic acid, oxalic acid, malic acid, succinic acid, malonic acid, propionic acid, fumaric acid, ~-ketoglutaric acidl glutaric acid and maleic acid.
The advantageous choice of a purine or pyrimidine is aimed at the phytosanitary agent containing at least one of the following compounds in the form of adenine, guanine and hypoxanthine (purines), cytosine, thymine and uracil (pyrimidines) or derivatives, especially nucleo-sides, nucleotides and salts thereof.
When vitaminY are employed, optimization can be carried out by selecting at least one vitamin in the form of thiamine, biotin, nicotinic acid, Ca pantothenate, pyridoxine hydrochloride, riboflavin, para-aminobenzoic acid, retinol palmitate (retinol), choline, cyanoco-balamin (vitamin Bl2) and folic acid or derivatives, salts or precur~ors thereof. In this connection, it is prefer-able for the vitamins pyridoxine hydrochloride, ribo-flavin, retinol palmitate, choline and folic acid each to be present in an amount of about 0.0001 to l mg~
especially 0.06 mg/l, the vitamins thiamine hydrochlor-ide, nicotinic acid and Ca pantothenate each to be present in an amount of about 0.05 mg/l, the vitamin para-aminobenzoic acid to be pre~ent in an amount of about 0.012 mg/l, the vitamin cyanocobalamin to be present in an amount of about 0.012 mg/l and the vitamin biotin to ~e present in an amount of about 0.0006 mg/l.
When the phytosanitary agent according to the invention is used, it is preferably previously converted into an aqueous form. The following concentration range is preferred in this connection: at least a single amino acid or car~oxylic acid each in an amount of about 0.01 to 10 mg/l, especially about 0.1 to 1 mg/l, at least a single purine or pyrimidine each in an amount of about 0.0001 to 1 mg/l, especially 0.006 mg/l, and at least a single vitamin each in an amount of about 0.0001 to 1 mg/l of aqueous agent- This phytosanitary agent "-.
:;, .. . , .. , : :
-` ~ 2029~77 ~ .
according to the invention is thus advantageously also de~igned such that the individual purines or pyrimidines are present in an amount of about 0.001 to 0.1 mg/l, especially 0.006 mg/l, the individual amino acids or S natural carboxylic acids are present in an amount of about 0.1 to 1 mg/l, especially 0.3 mg/l, the individual vitamins, pyridoxine hydrochloride, riboflavin, retinol palmitate, choline and folic acid are present in an amount of about 0.0002 to 1 mg/l, especially 0.06 mg~l, the individual vitamins thiamine hydrochloride, nicotinic acid and Ca pantothenate are present in an amount of about 0.05 mg/l, the vitamin para-aminobenzoic acid is present in an amount of about 0.012 mg/l, the vitamin cyanocobalamin is present in an amount of about 0.0012 mg/l and the vitamin biotin is present in an amount of about 0.0006 mg/l.
It may be advantageous in individual cases for the phytosanitary agent to be employed encapsulated. It is not sub~ect to any essential limitation with regard to the capsule wall. The latter should be enviro~mentally tolerated and, furthexmore, allow dosed emergence of the entrapped phytosanitary agent under the action of mois-ture. This makes its specific spread precisely at the site of action possible, ~o that there is no loss of action on those areas not colonized by plants. The encapsulation makes a long-term action possible. Suitable capsules which may be mentioned as example are those composed of liposomal materials such as of phospholipids.
The invention can be utilized with particular advantage in the treatment of plants and plant parts, especially for the prevention and control of plant diseases of biotic origin. Particularly important plant diseases which may be mentioned are Phytophthora infes~
tans tpotato blight), Botrytis cinerea (grey mould), Plasmopara viticola (downy mildew of grapevines), Uncin~
ula necator (powdery mildew of grapevines), Erysiphe graminis (powdery mildew of cereals), wheat smut (Tille~
tia sp.) and Pseudopeziza tracheiphila (red fire disease of grapevines). It is advantageous to employ the : . ~ , ' . ~ ' ';:
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-` ~ 2029~77 ..
phytosanitary agent according to the invention in i~di-vidual cases even where there is no phy~osanitary purpose but merely a desire to increase and ensure the yield of crop plants.
S The phytosanitary agents according to the inven-tion may in individual cases show in combination with compost extracts enhanced effect5 in controlling and inhibiting diseases and increasing yields and ensuring yields. This can entail the compost extract being mixed, Lmmediately after it has been obtained in aqueous form, with a phytosanitary agent according to the invention and then immediately applied. It is also possible to freeze-dry the compost extract and mix it with the phytosanitary agent according to the invention in powder form. The mixing ratio is not critical in this connection. There are other possibilities of utilizing the con~oint effect of compost extract and phytosanitary agent according to the invention. This can be achieved by feeding the phytosanitary agent according to the invention into the fermented organic substances during the extraction. With increasing extraction time, the constituents of the phytosanitary agent according to the invention are sub~ect to a certain breakdown or a certain transforma~
kion, so that the extracts obtained in this way and finally employed differ in their composition from that exhibited by the phytosanitary agent according to the invention alone. Despite this alteration, the biochemical effects are the same as achieved on use of the phytosani~
tary agent according to the invention alone. It depends on the individual case whether the activity of the phytosanitary agent according to the invention when used alone is better than that of the phytosanitary agent/
compost extract combination. Thus, overall, there is a wide variety of possible uses of ~he phytosanitary agent according to the invention.
A simple preliminary experiment can reveal which agent shows the optimal effect in the individual case.
The essential part is played in this by the host/parasite system used. Which of the abovementioned three cases . , . , , .
~ 2029~77 (control of fermentation, application at the same tLme as compost extracts and application alone) is particularly advantageous in the individual case can be determined by a conv~ntional screening methocl, attention being paid to the particular pest organism and to the particular crop plant. The test object used in each case is the plant to be protected with the appropriate pest organism.
The procedure for preparation of the compos~
extract~phytosanitary agent combination can be as fol-lows, for example: 10 parts by weight of an aqueouq solution of the phytosanitary agent according to the invention (about 0.3 mg of active substance in total in a litre of water) are used to submerge one part by weight of compost. It is possible in principle to employ all desired types of compo~t. Also especially suitable are commercially available composts such as the product "Biokuhdung" supplied by Backhus. The mixture of phyto~
sanitary agent and compost is shaken once after pouring together. The temperature during the extraction is preferably about 18 to 25C. It lasts about l to 30 days, depending on the host/parasite system. The completion of t~he extraction is followed by filtration through a fabric ~ ~-cloth or through another filter of similar pore size (not ;`~
sterile filtration). The extracts are used immediately { 25 after filtration or are preserved by freeze-drying or other methods and stored. The person skilled in the art ~ -is not in principle subject to any essential restrictions -~
in the obtaining of the compost extract/phytosanitary agent combination. The procedure described above can be modified in a wide variety of ways. ~-Specific encouragement of action-relevant micro~
organisms from the large number of microorganisms living in compost is possible by addiny specific phytosanitary;~ -~
agents according to the invention in connection with the compost extracts. It is possible in this way to control the fermentation process during the extraction, or an after-fermentation occurs. Application of the phyto-sanitary agent according to the invention alone or in combination with the compost extract directly to the .
' ' . , " ~ , ;
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''. . . -,:' :' : . ' ' ' . , .
~' 2029~77 leaves (or other plant parts~ brings about the phytosanitary effect in the fol:Lowing manner: a) specific encouragement of antagonists and/or of competitors and thus suppression of pest organisms; b) induced resis-tance, there being action either by the phytosanitaryagent according to the invention directly or by metabolic products of the encoura~ed microorganisms as inducers and c) interference with the mechanism of recognition between pest organism and crop plant b'y biochemical or physical reactions~ It can be e~ployed in aqueous form alone, in combination with aqueous compost extracts or compost pressed ~uices, in combination with resuspended compost lyophilisates and the like. Application is carried out, in particular, to above-ground plant parts or to seeds or to underground plant parts. Suitable for the treatment of seeds are the following application forms: seed baths in the treatment agents, coating with compost extracts, mixtures of the phytosanitary agent according to the invention with vehicles or use in capsules in the manner already described.
In the case of the Botrytis cinerea/bean host/
parasite system, a 60% reduction in attack was achieved with a pure compost extract, whereas an 80% reduction in attack was achieved with the compost extract/phytosani~
tary agent according to the in~ention combination (addition of the phytosanitary agent after obtaining the compost extract). The corresponding figures for the Phytophthora infestans/tomato host/parasite system were 80% and 90~ respectively (laboratory experLments). The strawberry/Botrytis cinerea, potato/Phytophthora infes-tans, barley/Erysiphe graminis, grapevine/Plasmopara viticola and grapevine/Uncinula necator host/parasite systems on treatment with a compost extract/
phytosanitary agent combination according to the inven~
tion showed figures of reductions in attack, compared with the untreated system, of 50%, 85%, 50 to 60%, 76 to 96~ and 70 to 80~ respectively and increased yield~ of 20 to 40 and 95% respectively for the strawberry/Botrytis cinerea and potato/ Phytophthora infestans hosttparasite system.
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., ; . ' " ". ` . ~ '' .''~ " . . .. :
:, :` -.. ,. - . ~ . ,.
; 2~29~77 The ctrawberry/Botrytis cinerea, potato/Phytophthora infestans and grape~ine/Plasmopara viticola host/parasite systems were investigated in open-field experLments, whereas the other host/parasite systems were tested in a glasshouse.
The result is that theladvantages achievable with the invention are that the treated plants and plant parts, such as seeds and fnlits, are protected from attack by diseases, the latter is ruled out or the pest organisms are inhibited or killed without the use of chemically objectionable biocides. In individual cases a repellent action on animal pests has also been ound (spider mites). Quantitative and qualitative improvements in the yields of crop plants can also be achieved with lS the agents according to the invention. The term "plant"
is intended in thi~ connection to be understood in its widest sense and to embrace living and dead plants and plant parts such as leaves, stems, fruits and seeds and underground organs and, for example, also wood products and the like.
The invention is to be explained hereinàfter in more detail by mean~ o various examples:
` :~ :
ExamE~e It was to be inves~i~a~ed whether the phytosanitary mixtures according to the invention dis~
play, alone or mixed with compost extracts, efficacy with regard to attack by the diseases Phytophthora infestans (potato blight) (plant: tomato) and Botrytis cinerea (grey mould) (plant: bean) in the affected plants. The following phytosanitary mixtures were used as a basis for this in both cases:
1) Phytosanitary aqueous solution according to the invention acting on Phytophthora infestans:
L-Aspartic acid 300 ~g/l L-Glutamic acid ~ ~g/l L-Histidine n ~g/l L-Arginine " ~g/l : ~: :, , ::::
.:: :~ :.: : . --~ ` 2029~77 L-Asparagine " ~g/l L-Ly ine " ~g/l :
L-~ethionins 300 ~g/l L-Threonine ~ ~g/l :
D-,L-Glutamine " ~g/l L-Proline ~ ~g/l : ~
h-Hydroxyproline ~ ~g/l . -~:
..:, ~ ,.,:
Uracil 6 ~g/l Hypoxanthine ~ ~g/l Riboflavin 60 ~g/l Retinol palmitate ~ ~g/l Choline " ~g/l Folic acid " ~g~
: ` ':',`" "
Para-aminobenzoic acid12 ~g/l Cyanocobalamin " ~g/l 2) Phytosanitary agent in aqueous compost extract acting .`
on Phyto~hthora inestans L-A~partic acid 300 ~g/l L-Glutamic acid " ~g/l L-Histidine " ~g/l L-Arginine " ~g/l D-,L-Valins " ~g/l L-Leucine " ~g/l L-Cystine " ~gJl L-Isoleucine " ~g/l Adenine sulphate 6 ~g/l Guanine hydrochloride" ~g/l Cytosine " ~g/l Thymine " yg/l Thiamine hydrochloride50 ~g/l Biotin 0.6 ~g/l Nicotinic acid sn ~g/l - . .;
` -' ; `2~2~77 - 14 - :
Ca pantothenate 50 ~g/l Pyridoxine hydrochloride 60 ~g/l
The po~sibilities, which have been identified above, of diminishing or elLminating or preventing, by composts and compost extracts, attack by diseases on plants and plant parts are not as yet satisfactory.
Various ~ubstance mixl:ures attributed with a phytosanitary action ha~e been di closed. Thus, SU-14 46 155 A describes an agent which contains an amino acid, a purine and a vitamin. It is used as additivo to the nutrient ~olution of tissue cultures in order to achieve regeneration of the plant organ~ and ~trengthen-ing of the young plants. It i~ not intended for plant protection and for application to above-ground plant parts. EP-A-0,253,714 deals with 2-componant mixture~
which have fungicidal activity and have a pyrLmidine derivative and alanine or a derivative thereof.
EP-A-0,044,224 is concerned with the combination of chlorocholine chloride and the "metabolic additivesl' ~including vitamins, amino acids, purines, pyrimidines, carboxylic acids). Neither chlorocholine chloride nor the metabolic additives alone are said to have a fungicidal action. DD-A-63,669 relates to a systemic fungicide which contains a combination of one part of a glycine deri~a-tive and 0.02 to 2 parts of an NB-substituted adenine.
2S Only one purine (adenine) and one amino acid (glycine) is cited. WO 79/008 38 relates to chemicals which can be used in agriculture, such as fungicides, herbicides and plant-growth regulators, and one or more of the following additives are cited: carbohydrates, organic acids (especially fatty acids), vitamins and coenzymes, purine and pyrimidine nucleosides and nucleotides, naturally occurring fats and oils, certain amino acids and, where these chemicals which can be used in agriculture are not themselves plant-growth regulators, such regulators.
DE-A-26 25 398 deals with an agent and a method for stimulating the germination of potatoes, the latter necessarily containing an amino acid in the form of cysteine and a purine in the form of kinetin.
2~29~77 ` 3 Summary of the invention:
The agents identified above give no clear teach-ing of how a phytosanitary agent might very generally be designed in order to open up the most wide ranging possible uses. This also applies to the possibilities, which ha~e been mentioned, of rleducing or eliminating by composts and compost e~tracts, attack .. .. . . . . ... .
by diseases on plants and plant: parts. Hence the ob~ect of the invention was to provide a remedy for this.
This is achieved according to the invention by a phytosanitary agent which is characterized in that it C contains I) natural carboxylic acids or their salts and/or at least two amino acids or their salts, II) purines and/or their derivatives, especially nucleo-~ides, nucleotides and salts thereof and/or pyrimidine~
an~/or their derivatives, especially nucleoside-~, nucleo-tides and salts thereof, and the salts of the purines and pyrimidines and III) vitamins or derivatives or precursors thereof, there being about 0.001 to 1 part by weight of a single compound of group II) and about 0.001 to 1 part by weight of a single compound of group III) for about 0.1 to 10 part~ by weight of a single compound of group I).
Accordingly, the central concept of the phyto-sanitary agent according to the invention is to employ at least two amino acids or their salts in the substance composition described qualitatively and quantitatively above. In this connection, it is preferable to use three, four or even more amino acids or their salts. This opens up the widest possible use of this agent with the desired phytosanitary effect. It has emerged that for certain uses it i~ possible to dispense with the requirement for at least two or more amino acid~, and this will be dealt with hereinafter.
The effects associated with the incorporation of at least two amino acids in the phytosanitary agent according to the inYention can b~ explained technologi-cally as follows:
2~2~77 The phytosanitary action of agents of this type on the surface of leaves is based on encouragement of non-pathogenic microorganism~. The encouraged microorganisms are able to suppress the pathogenic fungi or bacteria S either indirectly by competition for food or directly by antagonism and thus to elicit the phytosanitary effect.
Examples of possible microorganisms with a beneficial action known in this connect;ion are Pseudomonas and Bacillus species and various yeasts. Countless other microorganisms may be concerned. These microorganisms have different nutrient requirements, also with -regard to the various amino acids. Their nutrient xequirements are accordingly met by providing various amino acids, especially two or more, in the particular agent. Determination of the nutrient needs of all the microorganisms with a beneficial action on the surface of leaves (phyllosphere), taking account of the requirements of pathogenic microorganisms, is possible not only for a plant/pathogen systemD The determined nutrient combina-tion i~ then a compromise between the greatest possibleencouragement of the antagonists and of the competitors and the substantial avoidance o~ encouragement of patho-genic fungi and bacteria. The number of proteinogenous amino acids (21) is considerably larger than the number 25 of particularly suitable vitamins (11), purines (4), pyrimidines (3) or carboxylic acids (11) if the pre-cursors and derivatives are let out of account. Thus t the probability that two or more amino acids are advan-tageous i-~ considerably greater than in the case of vitamins, purines, pyrimidines or carboxylic acids. It is furthermore known that phyllosphere microorganisms live in a close biotic community with the plant. However, there is massive excretion of amino acids by th~ plants -both via roots and via leaves. The amino acids play an35 important part in the evolutionary adaptation of micro-organisms to the specific conditions of the surface of leaves. This might have led to the par~icular amino acid needs of phyllosphere microorganisms.
The invention particularly relates to the use of . ~,, 2~29~77 the phytosanitary agent according to the invention, which i~ described above, for the t:reatment of above-ground plant parts and harvested proclucts, especially for the prevention and control of plant dis~ases of biotic origin with a view to increasing ancl ensuring yields. It is particularly advantageous in this area of use, as desc-ribed hereinafter, to employ, mixed with the agent according to the invention, fermentation products from plants and plant residues, marine brown algae, animal residues or mixtures thereof, enriched with micro-organisms, especially bacteria, yeasts, fungi and single-C cell algae. Within the scope of these advantageous - possible use~ twith and without fermentation products~, `
the value of the invention is particularly evident when the particular agent is used to control Phytophthora infestans, Botrytis cinerea, Plasmopara viticola, Erysiphe graminis, Uncinula necator, Tilletia sp. and Pseudopeziza tracheiphila.
If fermentation products are employed mixed with the phytosanitary agent according to the invention, the mixing ratio does not normally play a crucial part in this connection. As a rough guideline, a mixing ratio, based on dry matter, of about l part by weight of phyto-~anitary agent according to the invention to 100 to lO,000, especially 300 to 3000, parts by weight of fermentation product, based on dry matter, might be mentioned. -~ ` -It ha~ emerged, in the advantageous areas of use, mentioned above, for the treatment of above-ground plant parts and harvested products, especially for the preven-tion and control of plant diseases of biotic origin with a view to increasing and ensuring yields, and with inclusion of the fermentation products and the like, especially for controlling Phytophthora infestans, Botrytis cinexea, Plasmopara viticola, Erysiphe graminis, Uncinula necator, Tilletia sp. and Pseudopeziza tracheiphila, that satisfactory effects can be achieved in this connection even if the requirement, described above, to employ in the phytosanitary agent according to :- .,: ~ ', '' :- ~ 2029~77 the invention at least two or more amino acids is dispensed with and the composition according to the invention contains only one amino acid or its salt.
Accordingly, the invention is also intended to relate to S the use of a phytosanitary agent of the composition, described above, of components I), II) and III), in which cnly one amino acid or its ~alt is employed.
On the basis of the outline conditions identified above, the procedure for putting the present invention into practice is preferably as follows~
If the phytosanitary agent according to the invention contains a single compound of group I), its amount is preset and on its ba~is, taking account of the outline conditions identified above, the particular amount of the individual compounds of group II) and III) is determined. If group I) embraces several compounds, it is advisable to use as a basis that individual compound which occupies a central position in terms of weight within group I). In the case where two or more compounds of group I) are present in the phytosanitary agent according to the invention, it i~ expedient to use as a ~asi~ the mean thereof. Each individual compound o groups II) and III) is related, in the identified range of amounts, with the amount of group I) used as a basis.
C 25 This means that, for example, there is from group II) 0.001 to 1 part by weight of a single compound A), 0.001 to 1 part by weight of a single compound B) etc. for 0.1 to 10 parts by weight of the preset amount of a compound of group I).
It is preferable to use about 0.1 to 5 parts by weight, especially about 0.5 to 5 parts by weight, of a single compound of group I) as a basis. The following amino acids are preferred: L-aspartic acid, L-glutamic acid, L-histidine, L-arginine, L-alanine, L-serine, D-and/or L-tryptophan, L-tyrosine, D- and/or L-phenyl-alanine, L-asparagine, L-ly~ine, L-methionine, L-threon-ine, D- and/or L-glutamine, L-proline, L-hydroxyproline, D- and/or L-~aline, L-leucine, L-glycine, L-cystine and L-isoleucine. When carboxylic acids are included, it is :,~-.,.,, preferable for the agent according to the invention to contain at least one of the following natural carboxylic acids or their salts: pyruvic acid, lactic acid, oxalic acid, malic acid, succinic acid, malonic acid, propionic acid, fumaric acid, ~-ketoglutaric acidl glutaric acid and maleic acid.
The advantageous choice of a purine or pyrimidine is aimed at the phytosanitary agent containing at least one of the following compounds in the form of adenine, guanine and hypoxanthine (purines), cytosine, thymine and uracil (pyrimidines) or derivatives, especially nucleo-sides, nucleotides and salts thereof.
When vitaminY are employed, optimization can be carried out by selecting at least one vitamin in the form of thiamine, biotin, nicotinic acid, Ca pantothenate, pyridoxine hydrochloride, riboflavin, para-aminobenzoic acid, retinol palmitate (retinol), choline, cyanoco-balamin (vitamin Bl2) and folic acid or derivatives, salts or precur~ors thereof. In this connection, it is prefer-able for the vitamins pyridoxine hydrochloride, ribo-flavin, retinol palmitate, choline and folic acid each to be present in an amount of about 0.0001 to l mg~
especially 0.06 mg/l, the vitamins thiamine hydrochlor-ide, nicotinic acid and Ca pantothenate each to be present in an amount of about 0.05 mg/l, the vitamin para-aminobenzoic acid to be pre~ent in an amount of about 0.012 mg/l, the vitamin cyanocobalamin to be present in an amount of about 0.012 mg/l and the vitamin biotin to ~e present in an amount of about 0.0006 mg/l.
When the phytosanitary agent according to the invention is used, it is preferably previously converted into an aqueous form. The following concentration range is preferred in this connection: at least a single amino acid or car~oxylic acid each in an amount of about 0.01 to 10 mg/l, especially about 0.1 to 1 mg/l, at least a single purine or pyrimidine each in an amount of about 0.0001 to 1 mg/l, especially 0.006 mg/l, and at least a single vitamin each in an amount of about 0.0001 to 1 mg/l of aqueous agent- This phytosanitary agent "-.
:;, .. . , .. , : :
-` ~ 2029~77 ~ .
according to the invention is thus advantageously also de~igned such that the individual purines or pyrimidines are present in an amount of about 0.001 to 0.1 mg/l, especially 0.006 mg/l, the individual amino acids or S natural carboxylic acids are present in an amount of about 0.1 to 1 mg/l, especially 0.3 mg/l, the individual vitamins, pyridoxine hydrochloride, riboflavin, retinol palmitate, choline and folic acid are present in an amount of about 0.0002 to 1 mg/l, especially 0.06 mg~l, the individual vitamins thiamine hydrochloride, nicotinic acid and Ca pantothenate are present in an amount of about 0.05 mg/l, the vitamin para-aminobenzoic acid is present in an amount of about 0.012 mg/l, the vitamin cyanocobalamin is present in an amount of about 0.0012 mg/l and the vitamin biotin is present in an amount of about 0.0006 mg/l.
It may be advantageous in individual cases for the phytosanitary agent to be employed encapsulated. It is not sub~ect to any essential limitation with regard to the capsule wall. The latter should be enviro~mentally tolerated and, furthexmore, allow dosed emergence of the entrapped phytosanitary agent under the action of mois-ture. This makes its specific spread precisely at the site of action possible, ~o that there is no loss of action on those areas not colonized by plants. The encapsulation makes a long-term action possible. Suitable capsules which may be mentioned as example are those composed of liposomal materials such as of phospholipids.
The invention can be utilized with particular advantage in the treatment of plants and plant parts, especially for the prevention and control of plant diseases of biotic origin. Particularly important plant diseases which may be mentioned are Phytophthora infes~
tans tpotato blight), Botrytis cinerea (grey mould), Plasmopara viticola (downy mildew of grapevines), Uncin~
ula necator (powdery mildew of grapevines), Erysiphe graminis (powdery mildew of cereals), wheat smut (Tille~
tia sp.) and Pseudopeziza tracheiphila (red fire disease of grapevines). It is advantageous to employ the : . ~ , ' . ~ ' ';:
. ~ - . . .
.. . . ..
. :
-` ~ 2029~77 ..
phytosanitary agent according to the invention in i~di-vidual cases even where there is no phy~osanitary purpose but merely a desire to increase and ensure the yield of crop plants.
S The phytosanitary agents according to the inven-tion may in individual cases show in combination with compost extracts enhanced effect5 in controlling and inhibiting diseases and increasing yields and ensuring yields. This can entail the compost extract being mixed, Lmmediately after it has been obtained in aqueous form, with a phytosanitary agent according to the invention and then immediately applied. It is also possible to freeze-dry the compost extract and mix it with the phytosanitary agent according to the invention in powder form. The mixing ratio is not critical in this connection. There are other possibilities of utilizing the con~oint effect of compost extract and phytosanitary agent according to the invention. This can be achieved by feeding the phytosanitary agent according to the invention into the fermented organic substances during the extraction. With increasing extraction time, the constituents of the phytosanitary agent according to the invention are sub~ect to a certain breakdown or a certain transforma~
kion, so that the extracts obtained in this way and finally employed differ in their composition from that exhibited by the phytosanitary agent according to the invention alone. Despite this alteration, the biochemical effects are the same as achieved on use of the phytosani~
tary agent according to the invention alone. It depends on the individual case whether the activity of the phytosanitary agent according to the invention when used alone is better than that of the phytosanitary agent/
compost extract combination. Thus, overall, there is a wide variety of possible uses of ~he phytosanitary agent according to the invention.
A simple preliminary experiment can reveal which agent shows the optimal effect in the individual case.
The essential part is played in this by the host/parasite system used. Which of the abovementioned three cases . , . , , .
~ 2029~77 (control of fermentation, application at the same tLme as compost extracts and application alone) is particularly advantageous in the individual case can be determined by a conv~ntional screening methocl, attention being paid to the particular pest organism and to the particular crop plant. The test object used in each case is the plant to be protected with the appropriate pest organism.
The procedure for preparation of the compos~
extract~phytosanitary agent combination can be as fol-lows, for example: 10 parts by weight of an aqueouq solution of the phytosanitary agent according to the invention (about 0.3 mg of active substance in total in a litre of water) are used to submerge one part by weight of compost. It is possible in principle to employ all desired types of compo~t. Also especially suitable are commercially available composts such as the product "Biokuhdung" supplied by Backhus. The mixture of phyto~
sanitary agent and compost is shaken once after pouring together. The temperature during the extraction is preferably about 18 to 25C. It lasts about l to 30 days, depending on the host/parasite system. The completion of t~he extraction is followed by filtration through a fabric ~ ~-cloth or through another filter of similar pore size (not ;`~
sterile filtration). The extracts are used immediately { 25 after filtration or are preserved by freeze-drying or other methods and stored. The person skilled in the art ~ -is not in principle subject to any essential restrictions -~
in the obtaining of the compost extract/phytosanitary agent combination. The procedure described above can be modified in a wide variety of ways. ~-Specific encouragement of action-relevant micro~
organisms from the large number of microorganisms living in compost is possible by addiny specific phytosanitary;~ -~
agents according to the invention in connection with the compost extracts. It is possible in this way to control the fermentation process during the extraction, or an after-fermentation occurs. Application of the phyto-sanitary agent according to the invention alone or in combination with the compost extract directly to the .
' ' . , " ~ , ;
.
''. . . -,:' :' : . ' ' ' . , .
~' 2029~77 leaves (or other plant parts~ brings about the phytosanitary effect in the fol:Lowing manner: a) specific encouragement of antagonists and/or of competitors and thus suppression of pest organisms; b) induced resis-tance, there being action either by the phytosanitaryagent according to the invention directly or by metabolic products of the encoura~ed microorganisms as inducers and c) interference with the mechanism of recognition between pest organism and crop plant b'y biochemical or physical reactions~ It can be e~ployed in aqueous form alone, in combination with aqueous compost extracts or compost pressed ~uices, in combination with resuspended compost lyophilisates and the like. Application is carried out, in particular, to above-ground plant parts or to seeds or to underground plant parts. Suitable for the treatment of seeds are the following application forms: seed baths in the treatment agents, coating with compost extracts, mixtures of the phytosanitary agent according to the invention with vehicles or use in capsules in the manner already described.
In the case of the Botrytis cinerea/bean host/
parasite system, a 60% reduction in attack was achieved with a pure compost extract, whereas an 80% reduction in attack was achieved with the compost extract/phytosani~
tary agent according to the in~ention combination (addition of the phytosanitary agent after obtaining the compost extract). The corresponding figures for the Phytophthora infestans/tomato host/parasite system were 80% and 90~ respectively (laboratory experLments). The strawberry/Botrytis cinerea, potato/Phytophthora infes-tans, barley/Erysiphe graminis, grapevine/Plasmopara viticola and grapevine/Uncinula necator host/parasite systems on treatment with a compost extract/
phytosanitary agent combination according to the inven~
tion showed figures of reductions in attack, compared with the untreated system, of 50%, 85%, 50 to 60%, 76 to 96~ and 70 to 80~ respectively and increased yield~ of 20 to 40 and 95% respectively for the strawberry/Botrytis cinerea and potato/ Phytophthora infestans hosttparasite system.
, .
: .
., ; . ' " ". ` . ~ '' .''~ " . . .. :
:, :` -.. ,. - . ~ . ,.
; 2~29~77 The ctrawberry/Botrytis cinerea, potato/Phytophthora infestans and grape~ine/Plasmopara viticola host/parasite systems were investigated in open-field experLments, whereas the other host/parasite systems were tested in a glasshouse.
The result is that theladvantages achievable with the invention are that the treated plants and plant parts, such as seeds and fnlits, are protected from attack by diseases, the latter is ruled out or the pest organisms are inhibited or killed without the use of chemically objectionable biocides. In individual cases a repellent action on animal pests has also been ound (spider mites). Quantitative and qualitative improvements in the yields of crop plants can also be achieved with lS the agents according to the invention. The term "plant"
is intended in thi~ connection to be understood in its widest sense and to embrace living and dead plants and plant parts such as leaves, stems, fruits and seeds and underground organs and, for example, also wood products and the like.
The invention is to be explained hereinàfter in more detail by mean~ o various examples:
` :~ :
ExamE~e It was to be inves~i~a~ed whether the phytosanitary mixtures according to the invention dis~
play, alone or mixed with compost extracts, efficacy with regard to attack by the diseases Phytophthora infestans (potato blight) (plant: tomato) and Botrytis cinerea (grey mould) (plant: bean) in the affected plants. The following phytosanitary mixtures were used as a basis for this in both cases:
1) Phytosanitary aqueous solution according to the invention acting on Phytophthora infestans:
L-Aspartic acid 300 ~g/l L-Glutamic acid ~ ~g/l L-Histidine n ~g/l L-Arginine " ~g/l : ~: :, , ::::
.:: :~ :.: : . --~ ` 2029~77 L-Asparagine " ~g/l L-Ly ine " ~g/l :
L-~ethionins 300 ~g/l L-Threonine ~ ~g/l :
D-,L-Glutamine " ~g/l L-Proline ~ ~g/l : ~
h-Hydroxyproline ~ ~g/l . -~:
..:, ~ ,.,:
Uracil 6 ~g/l Hypoxanthine ~ ~g/l Riboflavin 60 ~g/l Retinol palmitate ~ ~g/l Choline " ~g/l Folic acid " ~g~
: ` ':',`" "
Para-aminobenzoic acid12 ~g/l Cyanocobalamin " ~g/l 2) Phytosanitary agent in aqueous compost extract acting .`
on Phyto~hthora inestans L-A~partic acid 300 ~g/l L-Glutamic acid " ~g/l L-Histidine " ~g/l L-Arginine " ~g/l D-,L-Valins " ~g/l L-Leucine " ~g/l L-Cystine " ~gJl L-Isoleucine " ~g/l Adenine sulphate 6 ~g/l Guanine hydrochloride" ~g/l Cytosine " ~g/l Thymine " yg/l Thiamine hydrochloride50 ~g/l Biotin 0.6 ~g/l Nicotinic acid sn ~g/l - . .;
` -' ; `2~2~77 - 14 - :
Ca pantothenate 50 ~g/l Pyridoxine hydrochloride 60 ~g/l
3) Phytosanitary agent in aqueous com~ost extract acting on Botrytis cinerea : ::~
L-Aspartic acid 300 ~g~
L-Glutamic acid " ~g/l . -.-L-~istidine " ~g~
L-Arginine " ~g/l . -~
D-,L-Valine " ~g/l . :.
L-Leucine " ~g/l C ; L-Cyqtine " ~g~
L-IsQleucine " ~g~
: -: . -Adenine sulphate 6 ~g/l Guanine hydrochloride " ~g/l Cyto-~ine . " yg/l Thymine " ~g/l Thiamine hydrochloride 50 ~g/l Biotin 0.6 ~g/l ` Nicotinic acid 50 ~g/l Ca pantothenate 50 ~g/l Pyridoxine hydrochloride 60 ~g/l ~'
L-Aspartic acid 300 ~g~
L-Glutamic acid " ~g/l . -.-L-~istidine " ~g~
L-Arginine " ~g/l . -~
D-,L-Valine " ~g/l . :.
L-Leucine " ~g/l C ; L-Cyqtine " ~g~
L-IsQleucine " ~g~
: -: . -Adenine sulphate 6 ~g/l Guanine hydrochloride " ~g/l Cyto-~ine . " yg/l Thymine " ~g/l Thiamine hydrochloride 50 ~g/l Biotin 0.6 ~g/l ` Nicotinic acid 50 ~g/l Ca pantothenate 50 ~g/l Pyridoxine hydrochloride 60 ~g/l ~'
4) Phytosanitary agent in aqueous compost extract acting on Plasmopara viticola and Uncinula necator of grapevine.
L-Aspartic acid 300 ~g/l :
L~Glutamic acid " ~g/l L-Histidine " ~g/l L-Arginine " ~g/l D-,L-Valine " ~g/l L-Leucine ~ ~g/l L-Cystine " ~g/l L-Isoleucine " ~g/l ' Adenine sulphate 6 ~g/l : -~
Guanine hydrochloride 6 ~g/l : ~ :
~ ~ 2029~77 ~ .
Cytosine 6 /-g/l ;-~
Thymine " ~g/l Riboflavin 60 ~g/l Retinol palmita~e " ~g/l S Choline " ~g/l Folic acid " ~g/l ;~- ~
Para-aminobenzoic acid 12 ~g/l - `
Cyanocobalamin " ~g/l -~
Leaves were obtained as follows: bush kidney ~ `- 10 beans c.v. Marona were grown in a glasshouse. About 14 day~ were estimated for the use of primary leaves in the test, and about 3 to 4 weeks were estimated in the ca~e of secondary leaves. After this, indi~idual leave~ of equal age were cut off and placed in a dish con~aining `~`
water-impregnated blotting paper. Particular value was placed on an absolutely dry leaf surface of the bean leaves. Growing of the tomato plants took distinctly longer, about 5 to 6 weeks.
Inoculation on tomato leaves was carried out with a suspension of 70,000 sporangia per ml using a pump ~ -~
sprayer on the underside of the leaves. The temperature ~`
was reduced to about 12 to 14C for about 12 to 24 hours after inoculation in order to ensure ~p~i~um hatching of the zoospores and thus successful infection. For 7 subsequent days a temperature of about 20C during the day and 17C during the night was maintained with a ~`
light/dark alternation until evaluation. Botrytis in-oculation was carried out at the same time as application -~
of the extracts. In this case, to one drop of compost extract/phytosanitary agent of 0.015 ml was added the same amount of a spore suspension (106/ml in 0.5 - 15 malt ~ -~
extract solution). :
Extract was obtained as follows: the particular phytosanitary agent (in aqueous form) was diluted 1:10. ;~
10 parts by weight of this were used to submerge one part of compost. This mixture was vigorously shaken once after pouring together and then once each week. The extraction ~ 2~29~77 ~
',-: .: ~. .
conditions with regard to temperature and illumination corresponded to the experimental conditions. The amount of extract required for the l:reatment was prepared by filtration of the mixture, which had previously been freshly stirred, through a fabric cloth or coffee filter. ; `~
In order also to detect contributory actions from induced resistance, the pure pllytosanitary agent a~ well as the extract/pure phytosanitary agent mixture was ~`
applied to the intact plant. For this purpose, tomato plants were sprayed until dripping wet with the compost extract~phytosanitary agent 23 and in order to ensure a good possibility of survival and establishment of the microorganisms thereby applied on the phyllosphere and stored for three days in a climatized chamber with very high humidity (20C during the day, 18C during the night; dark period 7.00 to 20.00 h). One control used was a water treatment (with 0.5 - 1% malt extract for Botrytis), and other controls used for Phvtophthora were application of the fresh phytosanitary agents 1) and 2), by which means it is possible to estimate the direct effect of the phytosanitary agent on ths development of the disease.
The evaluation was carried out on the tomato leaves treated with phytosanitary agent 1) and 2) by a scoring in percentages, using a scoring system of C. James ~Canadian Plant Disease Survey 51 , 1971) as aid to estimation. In the case of Botrytis (plant: bean) the size of the leaf lesions and their enlargement beyond the limit of the drops was estimated. Analysis of variance and Duncan's test was càrried out for computation.
Result Phytophthora experiment (plant: tomato) The compost extract/phytosanitary agent mixture (mixture 2)) and the pure phytosanitary agent 1) dis-played a good action on Phytophthora. The action of pure r compost extract was distinctly exceeded. In terms of figures, the action may be said to be as follows:
~. ~ - ... ..
``: - . :
., ' '.~
.
2~2~77 ~ ~ ~
- 17 - ~-:
80% of untreated tomato leaves were affected by Phytophthora blight. The compc)st extracts alone brought cibout an 80~ reduction in attack, while the pure phyto~
sanitary agent l) and the agent 2) reduced attack to 5%.
Botrytis experiments (plant: bean) In this case phytosanitary agent 3) showed a particularly good action. A mixture of agent 3) with compost extracts led to an 85% reduction in attack, whereas the compost extracts alone reduced attack by Botrytis by only 60%.
:.. - :
C Ph~tophthora experiment (plant: potato, practical experi-ment) `
Application to the open field was carried out in the form of spray treatments which were repeated every 7 to 10 days during the vegetation period.
The phytosanitary agent l) showed a similar action to pure compost extracts and reduced attack by Phytophthora by about 45%. The mixture of compost extract and phytosanitary agent (2) reduced attack by 80%.
Experiment in an open vineyard The phytosanitary agent 4) showed a good action in experiments in a vineyard. Using this agent to spray ~' grapevines caused a reduction in attack by the powdery mildew fungus of more than 50%. Scoring of the attack by red fire disease (Pseudopeziza tracheiphila~ showed a significant reduction in attack by this disease of about 30%. ~ :
.
L-Aspartic acid 300 ~g/l :
L~Glutamic acid " ~g/l L-Histidine " ~g/l L-Arginine " ~g/l D-,L-Valine " ~g/l L-Leucine ~ ~g/l L-Cystine " ~g/l L-Isoleucine " ~g/l ' Adenine sulphate 6 ~g/l : -~
Guanine hydrochloride 6 ~g/l : ~ :
~ ~ 2029~77 ~ .
Cytosine 6 /-g/l ;-~
Thymine " ~g/l Riboflavin 60 ~g/l Retinol palmita~e " ~g/l S Choline " ~g/l Folic acid " ~g/l ;~- ~
Para-aminobenzoic acid 12 ~g/l - `
Cyanocobalamin " ~g/l -~
Leaves were obtained as follows: bush kidney ~ `- 10 beans c.v. Marona were grown in a glasshouse. About 14 day~ were estimated for the use of primary leaves in the test, and about 3 to 4 weeks were estimated in the ca~e of secondary leaves. After this, indi~idual leave~ of equal age were cut off and placed in a dish con~aining `~`
water-impregnated blotting paper. Particular value was placed on an absolutely dry leaf surface of the bean leaves. Growing of the tomato plants took distinctly longer, about 5 to 6 weeks.
Inoculation on tomato leaves was carried out with a suspension of 70,000 sporangia per ml using a pump ~ -~
sprayer on the underside of the leaves. The temperature ~`
was reduced to about 12 to 14C for about 12 to 24 hours after inoculation in order to ensure ~p~i~um hatching of the zoospores and thus successful infection. For 7 subsequent days a temperature of about 20C during the day and 17C during the night was maintained with a ~`
light/dark alternation until evaluation. Botrytis in-oculation was carried out at the same time as application -~
of the extracts. In this case, to one drop of compost extract/phytosanitary agent of 0.015 ml was added the same amount of a spore suspension (106/ml in 0.5 - 15 malt ~ -~
extract solution). :
Extract was obtained as follows: the particular phytosanitary agent (in aqueous form) was diluted 1:10. ;~
10 parts by weight of this were used to submerge one part of compost. This mixture was vigorously shaken once after pouring together and then once each week. The extraction ~ 2~29~77 ~
',-: .: ~. .
conditions with regard to temperature and illumination corresponded to the experimental conditions. The amount of extract required for the l:reatment was prepared by filtration of the mixture, which had previously been freshly stirred, through a fabric cloth or coffee filter. ; `~
In order also to detect contributory actions from induced resistance, the pure pllytosanitary agent a~ well as the extract/pure phytosanitary agent mixture was ~`
applied to the intact plant. For this purpose, tomato plants were sprayed until dripping wet with the compost extract~phytosanitary agent 23 and in order to ensure a good possibility of survival and establishment of the microorganisms thereby applied on the phyllosphere and stored for three days in a climatized chamber with very high humidity (20C during the day, 18C during the night; dark period 7.00 to 20.00 h). One control used was a water treatment (with 0.5 - 1% malt extract for Botrytis), and other controls used for Phvtophthora were application of the fresh phytosanitary agents 1) and 2), by which means it is possible to estimate the direct effect of the phytosanitary agent on ths development of the disease.
The evaluation was carried out on the tomato leaves treated with phytosanitary agent 1) and 2) by a scoring in percentages, using a scoring system of C. James ~Canadian Plant Disease Survey 51 , 1971) as aid to estimation. In the case of Botrytis (plant: bean) the size of the leaf lesions and their enlargement beyond the limit of the drops was estimated. Analysis of variance and Duncan's test was càrried out for computation.
Result Phytophthora experiment (plant: tomato) The compost extract/phytosanitary agent mixture (mixture 2)) and the pure phytosanitary agent 1) dis-played a good action on Phytophthora. The action of pure r compost extract was distinctly exceeded. In terms of figures, the action may be said to be as follows:
~. ~ - ... ..
``: - . :
., ' '.~
.
2~2~77 ~ ~ ~
- 17 - ~-:
80% of untreated tomato leaves were affected by Phytophthora blight. The compc)st extracts alone brought cibout an 80~ reduction in attack, while the pure phyto~
sanitary agent l) and the agent 2) reduced attack to 5%.
Botrytis experiments (plant: bean) In this case phytosanitary agent 3) showed a particularly good action. A mixture of agent 3) with compost extracts led to an 85% reduction in attack, whereas the compost extracts alone reduced attack by Botrytis by only 60%.
:.. - :
C Ph~tophthora experiment (plant: potato, practical experi-ment) `
Application to the open field was carried out in the form of spray treatments which were repeated every 7 to 10 days during the vegetation period.
The phytosanitary agent l) showed a similar action to pure compost extracts and reduced attack by Phytophthora by about 45%. The mixture of compost extract and phytosanitary agent (2) reduced attack by 80%.
Experiment in an open vineyard The phytosanitary agent 4) showed a good action in experiments in a vineyard. Using this agent to spray ~' grapevines caused a reduction in attack by the powdery mildew fungus of more than 50%. Scoring of the attack by red fire disease (Pseudopeziza tracheiphila~ showed a significant reduction in attack by this disease of about 30%. ~ :
.
Claims (14)
Patent claims
1. Phytosanitary agent, characterized in that it contains I) natural carboxylic acids or their salts and/or at least two amino acids or their salts, II) purines and/or their derivatives and/or pyrimidines and/or their derivatives and III) vitamins or derivatives or precursors thereof, there being about 0.001 to 1 part by weight of a single compound of group II) and about 0.001 to 1 part by weight of a single compound of group III) for about 0.1 to 10 parts by weight of a single compound of group I).
2. Agent according to Claim 1, characterized in that it contains at least three or four amino acids or their salts.
3. Agent according to Claim 1, characterized in that about 0.5 to 5 parts by weight of a single compound of group I) are present.
4. Agent according to Claim 1, 2 or 3, characterized in that it contains at least two of the following amino acids or salts thereof: L-aspartic acid, L-glutamic acid, L-histidine, L-arginine, L-alanine, L-serine, D- and/or L-tryptophan, L-tyrosine, D- and/or L-phenylalanine, L-asparagine, L-lysine, L-methionine, L-threonine, D-and/or L-glutamine, L-proline, L-hydroxyproline, D-and/or L-valine, L-leucine, L-glycine, L-cystine and L-isoleucine.
5. Agent according to any of Claims 1 to 4, charac-terized in that it contains at least one of the following natural carboxylic acids or their salts: pyruvic acid, lactic acid, oxalic acid, malic acid, succinic acid, malonic acid, propionic acid, fumaric acid, .alpha.-keto-glutaric acid, glutaric acid and maleic acid.
6. Agent according to at least one of Claims 1 to 5, characterized in that it contains at least one of the following compounds in the form of adenine, guanine and hypoxanthine (purines) and cytosine, thymine and uracil (pyrimidines) or salts thereof.
7. Agent according to at least one of Claims 1 to 6, characterized in that it contains at least one vitamin in the form of thiamine, biotin, nicotinic acid, Ca panto-thenate, pyridoxine, riboflavin, para-aminobenzoic acid, retinol palmitate, choline, cyanocobalamin (vitamin B12) and folic acid or in the form of derivatives and pre-cursors thereof.
8. Agent according to Claim 7, characterized in that it is in aqueous form.
9. Agent according to Claim 8, characterized in that it contains the individual amino acid (of at least two amino acids) in an amount of about 0.01 to 10 mg/l, especially about 0.1 to 1 mg/l, at least a single purine or pyrimidine in an amount of about 0.0001 to 1 mg/l and at least a single vitamin in an amount of about 0.0001 to 1 mg/l of aqueous agent.
10. Agent according to Claim 9, characterized in that the individual purines or pyrimidines are present in an amount of about 0.001 to 0.1 mg/l, especially 0.006 mg/l, the individual amino acids or natural carboxylic acids are present in an amount of about 0.1 to l mg/l, espe-cially 0.3 mg/l, the individual vitamins, pyridoxine hydrochloride, riboflavin, retinol palmitate, choline and folic acid are present in an amount of about 0.0002 to 1 mg/l, especially 0.06 mg/l, the individual vitamins thiamine hydrochloride, nicotinic acid and Ca panto-thenate are present in an amount of about 0.05 mg/l, the vitamin para-aminobenzoic acid is present in an amount of about 0.012 mg/l, the vitamin cyanocobalamin is present in an amount of about 0.0012 mg/l and the vitamin biotin is present in an amount of about 0.0006 mg/l.
11. Use of the agent according to at least one of the preceding claims for the treatment of above-ground plant parts and harvested products, especially for the preven-tion and control of plant diseases of biotic origin with a view to increasing and ensuring yields.
12. Use of the agent according to Claim 11, including fermentation products from plants and plant residues, marine brown algae, animal residues or mixtures thereof, enriched with microorganisms, especially bacteria, yeasts, fungi and single-cell algae.
13. Use according to Claim 11 or 12, including the possibility of employing a single amino acid or a salt thereof in the phytosanitary agent.
14. Use according to any of Claims 11 to 13 for controlling Phytophthora infestans, Botrytis cinerea, Plasmopara viticola, Erysiphe graminis, Uncinula necator, Tilletia sp. and Pseudopeziza tracheiphila.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3910061A DE3910061A1 (en) | 1989-03-28 | 1989-03-28 | PHYTOSANITANE MEDICINE AND ITS USE |
DEP3910061.8 | 1989-03-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2029877A1 true CA2029877A1 (en) | 1990-09-29 |
Family
ID=6377335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2029877 Abandoned CA2029877A1 (en) | 1989-03-28 | 1990-03-28 | Phytosanitary agent and its use |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0422147A1 (en) |
JP (1) | JPH03505585A (en) |
KR (1) | KR920700002A (en) |
CN (1) | CN1047191A (en) |
AU (1) | AU5334390A (en) |
BR (1) | BR9006157A (en) |
CA (1) | CA2029877A1 (en) |
DD (1) | DD298338A5 (en) |
DE (1) | DE3910061A1 (en) |
HU (1) | HUT56694A (en) |
PT (1) | PT93592A (en) |
WO (1) | WO1990011013A1 (en) |
ZA (1) | ZA902401B (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3933964C1 (en) * | 1989-10-11 | 1991-04-11 | Btc Biotechnik International Gmbh, 2050 Hamburg, De | |
GR1000953B (en) * | 1990-05-22 | 1993-03-16 | Btc Biotech Int | Fertilizing means and uses therefor |
JP2613136B2 (en) * | 1991-05-14 | 1997-05-21 | 株式会社コスモ総合研究所 | Plant growth promoter |
US6020288A (en) * | 1992-06-19 | 2000-02-01 | Nonomura; Arthur M. | Methods and compositions for enhancing cytochrome P450 in plants |
AU708417B2 (en) * | 1995-03-06 | 1999-08-05 | Andrew A. Benson | Methods and compositions for enhancing formyltetrahydropteroylpolyglutamate in plants |
JP2927269B2 (en) * | 1996-11-11 | 1999-07-28 | 味の素株式会社 | Plant root growth promoter |
WO2001056385A1 (en) * | 2000-02-02 | 2001-08-09 | Nonomura Arthur M | Methods and compositions for enhancing formyltetrahydropteroylpolyglutamate in plants |
JP2001302427A (en) * | 2000-04-25 | 2001-10-31 | Nok Corp | Plant growth accelerator and method for accelerating growth of plant by using the accelerator |
JP2003012417A (en) * | 2001-04-27 | 2003-01-15 | Ajinomoto Co Inc | Growth promoter for gramineous plants |
CN107683861A (en) * | 2016-08-05 | 2018-02-13 | 中国科学院微生物研究所 | A kind of composition for preventing and treating potato scab and preparation method thereof |
MX2019002410A (en) * | 2016-08-28 | 2019-09-18 | The State Of Israel Ministry Of Agriculture & Rural Development Agricultural Res Aro Volcani Center | Method of controlling fungal infections in plants. |
CN113711751B (en) * | 2021-09-07 | 2022-05-13 | 新洋丰农业科技股份有限公司 | Facility cultivation water and fertilizer integrated system and fertilizer application method |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD63669A (en) * | ||||
DE2625398A1 (en) * | 1976-06-05 | 1977-12-15 | Philips Patentverwaltung | Seed potato germination stimulation - with agents contg. cysteine, kinetin and calcium glycerophosphate and/or calcium pantothenate |
JPS55500166A (en) * | 1978-03-28 | 1980-03-27 | Michael James Sampson | |
ZA814783B (en) * | 1980-07-16 | 1982-07-28 | M Sampson | Disease control in plants |
IT1196465B (en) * | 1986-07-07 | 1988-11-16 | Montedison Spa | FUNGICIDE MIXTURES |
SU1446155A1 (en) * | 1987-04-02 | 1988-12-23 | Институт молекулярной биологии и биохимии АН КазССР | Method of producing regenerant plants of corn from tissue culture |
-
1989
- 1989-03-28 DE DE3910061A patent/DE3910061A1/en active Granted
-
1990
- 1990-03-28 EP EP90904830A patent/EP0422147A1/en not_active Withdrawn
- 1990-03-28 KR KR1019900702527A patent/KR920700002A/en not_active Application Discontinuation
- 1990-03-28 CA CA 2029877 patent/CA2029877A1/en not_active Abandoned
- 1990-03-28 JP JP2504931A patent/JPH03505585A/en active Pending
- 1990-03-28 PT PT93592A patent/PT93592A/en not_active Application Discontinuation
- 1990-03-28 ZA ZA902401A patent/ZA902401B/en unknown
- 1990-03-28 WO PCT/EP1990/000491 patent/WO1990011013A1/en not_active Application Discontinuation
- 1990-03-28 DD DD90339159A patent/DD298338A5/en not_active IP Right Cessation
- 1990-03-28 BR BR9006157A patent/BR9006157A/en not_active Application Discontinuation
- 1990-03-28 CN CN90104130A patent/CN1047191A/en active Pending
- 1990-03-28 AU AU53343/90A patent/AU5334390A/en not_active Abandoned
- 1990-03-28 HU HU902756A patent/HUT56694A/en unknown
Also Published As
Publication number | Publication date |
---|---|
PT93592A (en) | 1990-11-07 |
DE3910061C2 (en) | 1991-04-11 |
CN1047191A (en) | 1990-11-28 |
EP0422147A1 (en) | 1991-04-17 |
WO1990011013A1 (en) | 1990-10-04 |
AU5334390A (en) | 1990-10-22 |
BR9006157A (en) | 1991-08-06 |
JPH03505585A (en) | 1991-12-05 |
ZA902401B (en) | 1991-01-30 |
KR920700002A (en) | 1992-02-19 |
HUT56694A (en) | 1991-10-28 |
DE3910061A1 (en) | 1990-10-04 |
DD298338A5 (en) | 1992-02-20 |
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Legal Events
Date | Code | Title | Description |
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FZDE | Discontinued | ||
FZDE | Discontinued |
Effective date: 19940928 |