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Title:
PLANT PROTECTING COMPOSITION
Document Type and Number:
WIPO Patent Application WO/1987/000400
Kind Code:
A1
Abstract:
Compositions for treating and/or preventing plant diseases or regulating the growth of plants, as well as the preparation and use thereof. According to the process the compositions are prepared by contacting one or more active compounds for plant treatment with an alkyl methacrylate and a cross-linking inhibiting agent by energy transmission.

Inventors:
ODOR ZOLTAN (HU)
Application Number:
PCT/HU1986/000044
Publication Date:
January 29, 1987
Filing Date:
July 16, 1986
Export Citation:
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Assignee:
INNOFINANCE ALTALANOS INNOVACI (HU)
International Classes:
A01N3/04; A01N25/24; A01N37/06; (IPC1-7): A01N25/22
Foreign References:
DE3304457A11983-10-13
US3660071A1972-05-02
DE2105174A11971-08-19
FR2502054A11982-09-24
US4105793A1978-08-08
US4329360A1982-05-11
GB1354298A1974-06-05
Download PDF:
Claims:
- 22 -Claims
1. Process for preparing a substance for treating plants, ch racterized in that one or more active compounds for plant treatment /basic active material/ is contacted with an alkyl methacrylate, preferably methyl methacrylate and a cross linking inhibiting agent /inhibitor/ by energy transmission and, if desired, the product thus obtained /activ substance/ is dluted with water, wherein the ratio of the basic active material, alkyl methacrylate and inhibitor is 1:0,910:0,810. 2.
2. The process according to claim 2, characterized in that a substance for the treatment and /or prevention of plant diseases and /or for regulating the plant growth and /or for enhancing the ion supply of plants and /or wild repe'llant is prepared.
3. The process according to any of the claims 1 and 2, characteriz ed in that as basic active material a chemical active against plant pathogen fungi, insects, mites, viruses, bacteria and /or nematodes is used.
4. The process according to any of claims lto3, charac¬ t e riz e d in that as inhibitor hydroquinone is used.
5. The process according to any of claims lto4, ch arac t e r i z e d that the energy transmission is accomplished by heat, UV or laser irradiation, preferably under stirring.
6. The process according to any of claims lto5, char a c terized in that the basic active material, alkyl methacrylate and inhibitor are mixed and heated at 100 to 130 °C, preferably for 0,5 to 3 hours.
7. The process according to any of claims lto5, cha ra c terized in that the mixture of the basic active material , alkyl methacrylate and inhibitor is treated with UV light for 5 to 40 minutes at 10 to 80 °C.
8. The process according to any of claims lto5, charac terized in that the stirring is accomplished by bubbling nitrogen or carbon dioxid gas through the mixture.
9. The process according to any of claims lto5, cha r a c t erized in that the mixture of basic active material , alkyl methacryl and inhibitor is treated with laser rays.
10. The process according to any of claims lto9, charac terized in that fungicidal basic active material is selected from the group consisting of phtalimido derivatives, dithiocarbamates, disulfides, heterocyclic compounds, preferably benzimidazoles and triazines.
11. The process according to any of claims 1 to 10, ch r a t erized in that the fungicidal basic active material is selected from the group consisting of Zineb, Maneb, Mankozeb, Metiram, Me tarn, Propineb, TMTD, Dital imphos, Folpet, Captafol, Captan, Bitertanol, Benomyl, Bupirimat, 4butyl4Hl,2,4triazine, Dichlorbutrazol, Dithia Dodemorph, Ethirimol, Fenarimol, Fuberidazole, Hymexazol, Iprodion, Carbendazim, Carboxin, Chinomethionat, Nuarimol, 8oxichinolin sulph Pirohophos, Procymidon, copper oxyquinolate , Triadimophon, Triadimen Tridemorph, triphorin, Vinchlozolin, Zymoxanyl, Dichlofluanid, Dinocap Dodine, EphositeAl, Fentin acetate, Fentin hidroxid , Chlorothalonil , Methalaxyl, Nitrothalisopropyl, PolyoxinB, Thiophanat methyl, Dodem Bitertanol, Ephosit, Chlorothalonil, Cymoxanyl, Mantozeb, Dichlofluani Captan, Malathion, Dithalimphos and Dichlobutrazol.
12. The process according to any of claims lto9, charac te rized in that the insectlcidal basic active material is selected fro the group consisting of chlorinated hydrocarbons, phosphonic acid ester phosphoric acid esters, thiophosphoric acid derivatives, dithiophosphori acid derivatives, salycylic acid esters, thiolderivatives, carbamates and pyrethroids.
13. The process according to any of claims 1 to 10, char terized in that the insecticidal basic active material is selected from the group consisting of Endosulfan, Dienochlor, Kelevan, Lindan, Toxaphen 24 Butonate, Dichlorvos, Fonofos, Phosamidσn, Heptenophos, Chlorfen vinphos, Mevinphos, Monocrotophos, Trichlorfon, Bromophos, Diazinon, Phenitrothion, Fenthion, Chinalfos, Chlorpiriphos, Tetra chlorvinphos, Methyl parathiσn, Pirimiphos methyl, Triazophos, Dimethoat, Phenthoat, Phormothion, Phosalone, Phosmet, Malathion, Metidathion, Methylaziphos, Prothoat, Sulfotepp, Terbuphos, Phorate, Thiometon, Aldicarb, Dioxacarb, Carbaryl, Carbofuran, Mercaptodimet Methomyl, Oxamyl, Pirimicarb, Bioresmetrin, Zipermetrin, Deltametrin Phenvalerate, Phtalthrin, Tetrametrin, Pirethrin, Neopyramin, Pormeth DNOC, kartap, Pirimiphos methyl, Terbuphos, Dazomet, Diflubenzuron, Thiocyclam, Propoxur, Fenazox, Metamidophos, Pirimicarb and Methylpar athion .
14. The process according to any of claims lto9, charac t er ized in that the acaricidal basic active material is selected from the group consisting of Dinobuton, Tetrasul, Formothion, Dimethoat Thiometon, Malathion, Phosphothion, Fenthion, Tetradiphon, Zi exathin Fenbutatin oxide , Chlorpropylate and Amitrase .
15. The process according to any of claims lto9, chara t erized in that the plant growth regxdator is selected from the grou consisting of Etephon, gibberellic acid, Nphenyiphtalanic acid, alfa naphtyl acetic acid and betaindolyl butyric acid.
16. The process according to any of claims 1 to 9 for prepar¬ ing wild repellent , char acterized in that as basic active material at least one quinine salt, preferably hydrochloride is used.
17. The process according to any of clai s 1 to 9 for prepar ing dressing compositions, ch ar ac t erized in that as basic active material one or more of the chemicals listed in claims 10 to 15 are used.
18. Composition for plant treatment comprising one or more active compound /basic active material/ and alkyl methacrylate, prefera methyl methacrylate which is entirely or partly bound to the basic active material/s/ as well as 0,01 to 10 parts by weight of crosslinking inhibiting material /inhibitor/ based on 1 part by weight of alkyl methacrylate .
19. The composition according to claim 18, c h ar a c 5 te ri zed by containing as basic active material one or more pesticide insecticide, acaricide and nematocide and /or trace elements and regu lants.
20. The composition according to any of the claims 18 and 19, cha r acterize d in that the basic active material is 10 selected from the group consisting of dithiocarbamate s , disulfides, heterocyclic compounds and phtalimido derivatives.
21. The composition according to any of the claims 18 to 20, char act erized in that the basic active material is selected from the group consisting of Zineb, Maneb, Mankozeb, 15 Metiram, Metam, Propineb, TMTD, Ditalmimphos, Folpet, Captafol, Captan, Bitertanol, Benomyl, Bupirimet, 4buthyl4Hl,2,4triazine, Dichlorbutrazol, Dithianon, Dodemorph, Ethirimol, Fenarimol, Fuberidazole, Hymexazol, Iprodion, Carbendazim, Carboxin, Chino¬ methionat, Nuarimol, 8oxichinolin sulphate, Pirozophos, Procymidon, 20 copperoxyquinolate, Triadimophon, Triadimenol, Tridemorph, triphori Vinchlozolin, Zymoxanyl, Dichlofluanid, Dinocap, Dodine, EphositeAl, Fentin acetate, Fentin hidroxide , Chlorothalonil, Methalaxyl, Nitrothal isopropyl, PolyoxinB, Thiophenatmethyl, Dodemorph, Bitertanol, Ephosit, Chlorothalonil, Cymoxanyl, Mantozeb, Dichlofluanid, Captan, 25 Malathion, Dithalimphos and Dichlobutrazol.
22. The composition according to any of claims 18 and 19, cha r act erized in that the insecticidal basic active material is selected from the group consisting of chlorinated hydrocarbons, phosphonic acid esters, phosphoric acid esters, thiophosphoric acid 30 derivatives, dithiophosphoric acid derivatives, salycylic acid esters, thiol derivatives, carbamates and pyrethroids. 26 .
23. The composition according to any of claims 18 and 19, charact rized in that the acaricid&i basic active material is selected from the group consisting of Dinobuton, Tetrasul, Formothio Dimethoate, Thiometon, Malathion, Phosphothion, Fenthion, Tetradipho Zihexathin, Fenbutatin oxide , Chlorpropylate and Amitrase.
24. The composition according to any of claims 18 and 19, characterized in that the plant growth regulating basic active material is selected from the group consisting of Etephon, gibberellic acid, Nphenyl phtalanic acid, alfanaphtyl acetic acid and betaindolyl butyric acid.
25. The composition according to any of claims 18 and 19, characterized in that the repellant basic active material is at least one quinine salt, preferably hydrochloride and sulfate.
26. The composition according to any of claims 18 to 25, cha r acterized by containing additional auxiliaries, preferably emulsifiers, wetting agents, diluants, and microelement sources.
27. The composition according to any of claims 18 to 25, cha rac terized by containing the microelements magnesium, iron, zinc, manganese, boron, copper, molybdenum and cobalt, optional in the form of salt or chelate thereof.
28. Process for treating plants, ch ar ac terize din that a composition of any of claims 18 to 27 is applied on the surface of plant by conventional methods so that to cover at least 5 to 19 % of the said plant.
Description:
PLANT PROTECTING COMPOSITION

Technical field

The present invention relates to compositions for treating and /or preventing plant diseases or regulating the growth of plants , as well as to the preparation and use thereof.

Background art

Certain phytoparasitic insects are symbion with tissue parasitic fungi, e . g. Enarmonia formoson with the fungus Cytospora cincta, or the clearwing moths with the fungi Croptosporioptis malicor or Sphacropsis malorum. Other example s of such association are as follow s :

- Bark beetles /Scolitideae / and the fungus Pacidiella discolor ,

- Wood weavils /Hulobuis abietis / and different wood- rotting and Cytospora fungi,

- Apple clearwing /Sunantedon myoaefomis / and fungus Sphaeropsis malorum,

- Bark beetle /Scoytus / causing the destruction of white aim and the fungus Graphium ulmi.

While laying eggs , the insect can also get the spore s or living mycelia of parasitic fungi to the plant by its legs or excrement. Some parasitic fungi start their vital functions in places fret by the insect, in the phloem layers .

In case of shrubby trees , the plant pathogenic fungus penet into the xylem, the phloem and finally into the woody part of the plant.

The vital functions of the fungus develop already at 0 °C . The eggs o pathogenic insects laid on the fret or wounded plant surface atch in a few weeks. The worms penetrate into the plant tissues and the ba

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resp. , and live there until their total development. The life condition thereof can be facilitated by the presence of parasitic fungi brought in at the time of laying eggs , as the protein needs of the grub will be covered by the matured fungus . As a consequence , a malign proce is initiated in the plant tissue . The formation of dead tissues is promoted by the grub destroying the tissues responsible for the fluid transport, thus, disturbing the fluid supply.

The insect lives in the bark as worm through the winter and metamorphoses to nymph in the spring or early summer. After - wards the lower part of nymph gets extruded from the loose tissue and the imago emerges. After fertilization the imago returns to the same malign plant part or to other freshly wounded surfaces to lay the new eggs , thus , again introducing the spores and mycelia of the symbion, parasitic fungi and the circulation will go on. Different effects may cause plant injurie s , . like frost damages , bark etoliations caused by the sun, fractions caused by sno ice , cultivating tools , vibrators, etc . , open wounds , bites of animal damages by insects living in the plant tissues or open wounds caused by pruning. Ma lign surface injuries caused by fungi should also be considered. The se "open doors" provide an easy way for insects and parasitic fungi to penetrate into the plant and thus, to set the above circulation into motion.

At certain strains , e . g. currant clearwing /Synanthedo tpuliformis/ the infection can be promoted if the imago does not fly right after leaving the nymph "capsule" but copulates in a few hours and lays eggs immediately, usually at the area of "flight slit" . The worms start to fret at the slit and penetrate into the inside of cane and destroy greater and greater area therein. Accordingly, the livin time of the imago on the surface is very short, and the in vivo protec ion is hardly useful. In case of the aforesaid plant the only way of protection has been the removal and burning of canes .

In case of white aim the bark beetle is in permanent moving within the hadrome . Due to the rapid growth of Graphiu ulmi the fluid transportation vessels will be blocked , thus , resulting in a parti or total etiolation of the tree . The only way of defence has been fellin and total burning of the tree .

The above complex fungus -insect damages can be observed in cultures of potato , oil-seed plants , like sunflower, cereals and vineyards . For example , powdery mildew, blust and block-rust occur in cereal cultures together with the damages caused by the "whitening beetle" .

A large number of broad- spectrum insecticide s and fungicides have already been used against injury-parasitic fungi and the insects living in symbiosis therewith.

The known non-systemic insecticides possessed, however, surface activity only, i. e . their effect was limited only to controlling the imago or butterfly being in no contact with the plant. The effect on the parasitic fungi in symbiosis with the imago was of the same type .

In spite of the wide use of insecticides and fungicides , the diffusion of many plant diseases could not be controlled. For example , the phloem and bark destructive insects have spread over the tempera zone and caused substantial economic damage s in American and Europ countries , e . g. by leading to the destruction of primeval white alms , etc .

Disclosure of Invention

The present invention provides a process for preparing a material for use of plant treatment, characterized by contacting one or more compound used for plant treatment /in the followings basic active material/ with alkyl methacrylate , preferably methyl methacryl by the aid of energy transmission, in the presence of a cross-linking inhibiting agent /inhibitor/.

By using the process according to the invention, compositions for the treatment and /or prevention of plant diseases, the regulation of plant growth and /or enhancing the ion supply of plants and /or repelle may be obtained . As basic active material, fungicides, insecticides, nematocid acaricides, bactericides and /or antiviral chemical compounds, etc. m y be used.

Examples of insecticidal basic active materials are as follows: chlorinated hydrocarbons, phosphonic acid esters, phosphoric acid esters, thiophosphoric acid esters, dithiophosphoric acid esters, salycilic acid esters, thiolderivatives, carbamates and /or pyrethroids or compounds of other ' structure . Preferred active compounds are as listed herebelow: Endosulfan, Dienochlor, Kelevan, Lindan, Toxaphen, Butonate, Dichlorvos, Fonofos, Phosphamidon, Heptenophos, Chlorfen- vinphos, -Mevinphos, Moiiocrotophos, Trichlorfon, Bromphos, Diazinon

Phenitrothion, Fenthion, Chinalfos, Chlorpiriphos, Tetrachlorvinphos, Methylparathion, Pirimiphos -methyl, Triazophos, Dimethoat, Phenthoat Phormothion, Phosalone, Phosmet, Malathion, Metidathion, Methylazip Prothoat, Sulfotepp, Terbuphos, Phor te, Thiometon, Aldicarb, Dioxacarb, Carbaryl, Carbofuran, Merceptodimethur, Methomyl, Oxam

Pirimicarb, Bioresmetrin, Zipermetrin, Deltametrin, Phenvalerate , Phtalthrin, Tetrametrin, Pirothrin, Neopyramin, Pormothrin , DNOC, kartap, Purimiphos -methyl, Terbuphos, Dazomet, Diflubenzuron , Thiocyclam, Propoxur, Fenazox, Hetamidophos, Pirimicarb, Methyl - parathion and the analogues thereof.

As acarici^e, e. g.4,4-dichlorobenzyl acid isopropyl ester, Dinobuton, Tetrasul, Formothion, Dimethoate, Thiometan, Malathion, Phosphothion, Fenthion, Tetradiphon, Zihexathin, Fenbutatin oxide, Chlorpropylate , Amitrase and the like ma be used, preferably in a concentration of 0,015 to 0,2 % by weight.

As plant growth regulating agent, e. g. one or more compound

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selected from the group consisting of beta-indolylbutyric acid, alfa- -naphtyl acetic acid, etaphon and N-phenyl phtalamic acid may be used.

As fungicide , both the systemic and non- systemic fungicidal compounds may be used: the penetration of the compounds: is provided by the material obtained by the ineraction with the alkyl methacrylate and inhibitor.

The fungicides may be selected from the following groups of organic compounds: phtalimide derivatives , dithiocarbamates, disulf heterocyclic compounds , preferably benzimidazol derivatives, triazine e . g. benzimidazol- or triazyl -derivatives , copper- and sulphur -based fungicides , cyanoacetic acid derivatives or the mix tures thereof and the like.

Preferred and commercially available fungicides are listed herebelow: Zineb , Maneb, Mankozeb , Metiraϊn, Metam, Piropineb,

TMTD , D italmimpho s , Folpet, Captafol, Captan, Bitertanol , Benomyl , Bupirimat , 4-buthyl-4H-l , 2,4-triazine , Dichlorbutrazol , Dithianon, Dodemorph, Ethirimol, Fenarimol, Fuberidazole , Hymexazol, Fprodion Carbendazim, Carboxin, Chinomethionat, Nuarimol , 8-oxi-chinolin- -sulphate , Pirazophos , Proeymidon, copper -oxyquin late , Triadimeph

Triadimenol, Tridemorph, Triphorin, Vinchlozolin, Zymoxanyl , Dichlo Dinocap, Dodine , Ephosite-Al, Fentin acetate , Fentin hidroxide , Chlo thalonil, Methalaxyl, Nitrothal-isopropyl, Polyoxin-B , Thiophanate -m Dodemorph , Bitertanol, Triadimenol, Ephasit, Chlorothalonil , Mantoz Dichlofluanid , Captan, Malathion, Dithalimphos, Dichlobu trazol or the mixture of any of the above compositions or the analogs thereof.

According to the invention the preferred inhibitors may be the hydroquinon, hydroquinon-derivatives , ascorbic acid, phenol and phenol derivatives . These compounds , besides inhibiting the non-desir polymerization of the alkyl methacrylate , also possess a certain bacter effect.

The energy transmission can be accomplished e . g. by heat treatment, UV or laser irradiation, preferably under stirring.

If the energy transmission is carried out by heat treatment, the basic active material, the alkyl methacrylate and inhibitor are mixed and warmed up to 100 to 130 C . The treatment is carried out preferabl for 0,5 to 3 hours .

According to another embodiment of the invention, the mixture of alkyl methacrylate , the basic active material and inhibitor is treat¬ ed by UV irradiation for 5 to 60 minutes at 10 to 20 °C , preferably unde cooling. For this purpose , a quartz sound provided with a cooler and a quartz bulb working in the range of 3000 to 5000 A is placed into the reactor. In this case the stirring is accomplished with an inert gas , preferably nitrogen or carbon dioxide . By working without cooling, the reaction temperature will raise to about 80 C . According to another embodiment of the invention , the mixture of alkyl methacrylate , the basic active material and inhibitor are treat¬ ed by laser irradiation. For example in photochemical reactor, under strong water cooling and nitrogen stirring and using argon-ion 488 nm line at a performance of 1 W the reaction takes place in 2 to 3 hours . By using an apparatus of 4 W performance /6 laser lines enter the react area together/ the reaction time decreases to 30 to 40 minutes . This reaction mode eliminates the need of heat energy and the reaction can safely be controlled.

According to the invention the preferred ratio of the reactants is 0, 9 to 10 parts by weight of liquid alkyl methacrylate monomer and

0, 8 to 10 parts by weight of inhibitor to 1 part by weight of basic active material.

The process according to the invention provides a product by using energy transmission and known starting material , which has not been known and which can effectively be used as active ingredient plant protecting chemicals.

Another object of the invention is the composition for plant treatment consisting of one or more active compound "basic active masterial" , usual additives and an alkyl methacrylate , preferably met methacrylate which may be present in the form of partly or entirely bound to the active compound/s/, the said composition also containing a cross-linking inhibiting material /"inhibitor" / in an amount of 0,01 to 10 parts by weight to 1 part by weight of methacrylic acid ester.

The composition according to the invention may contain appropriate additives , auxiliaries an l other materials generally used in the plant protecting practice .

The object of the present invention is also a composition whi contains the product prepared from the basic active material, the al methacrylate and inhibitor by energy transmission, and 0, 001 to 5 % by weight of emulsifier, wetting agent and other auxiliaries .

The emulsifier is used preferably in the amount of 0, 1 to 5 % by weight. Examples of the emulsifiers are the tallow fat, ethoxyl fatty alcohol sulfonate tetramine /25 EtO/ alkylphenol-hatethox /fatty- alcohol sulfonate , 22 EtO/, casein. As wetting agent, propyleneglycol, polyethylene glycol or glycovet may be used. The use of 0, 001 to 0, 01 % by weight of wettin agent is sufficient.

By mixing the above product with carriers and diluants , re composition ready for use is obtained. For this purpose , water in the form of 0,2 to 10 % by weight emulsion may be used.

Another object of the invention is the use and mode of applic ion of the above compositions on damaged plant with curative effect o on healthy plants as preventive composition .

The composition may be formulated e . g. to the form of paste , viscous solution or aqueous dilutions /such as spray/.

As additive , pigments or pigment -containing materials may also be added to the composition, if labelling is needed . Such additives are e . g. the indatene derivatives , which are then degraded when explos to UV light.

The biological activity of the compositions according to the invention has been tested and established against plant diseases caused by different insects and fungi. Such diseases include e . g. the following - branch, carcinoma caused by Enarmonia formoson and the fungus Cytospora ciucta on apricot and peach,

- carcinoma caused by bark beetle /Schytus / and the fungus Phaciodella discolor on peer and apple trees ,

- "black car iαcma" caused by clearwing /Synanthedon mypaefonis / and Sphaeropsis malorum on apple and pear,

- carcinoma caused by.Nectria galligensa on pear and apple trees , etc.

The compositions according to the invention are especially effective against the grape -destructive fungus Entypa and different fungi of the genus Cytosporina, which have an important effect especially duri the cordon cultivation.

The use of the compositions according to the invention on vine e . g. may be accomplished as follows:

The essential requirement of protection is to eliminate the centres of infection. The shoots cut off and the decayed stocks should be removed from the vineyard and burned. The stock feeding the cordon possesses at least partly a decayed surface which makes the growth of fungi possible . The matured fungi form αallulose sporong iae which swell by the effect of rain and push out the spores . These spores are carried by the wind , insects and rain. As the above function is provided by the spring rains , the spores precipitate on the pruning wounds of

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cordon vine wherein the ideal conditions of fungus growth are provide The protection should be accomplished on the following grounds:

1/ The stock should be sprayed with an aqueous emulsion of the composition according to the invention /silicon-containing spray is preferred/. Consequently, the active ingredient kills the mycelia and spores of the fungi, while the silicon makes the stock hydrophobic and prevents the permeotion of water to the sporangine thus they beco unable to swell and push out the spores .

2/ After pruning, the cordon should be sprayed with a composi ion according to the invention containing a fungicide and an insecticide which is effective against Enarmonia formoson, thus stopping the "guttation" of the stub .

In case of infected cordons "washing sprinkling" should be used in the spring or fall with an aqueous form of the composition according to the invention, preferably with a 20 % dilution. When usin

"washing sprinkling" after pruning the "guttation" and accordingly the secondary fungus infection will be eliminated'.

The aqueous composition according to the present invention as spray on wound infections is recommended for the treatment of wounds made in winter or early spring. Spraying is preferred to perform at a average temperature of +5 °C only. It has been proved that the wound got cured and no injury occured .

The composition according to the invention may be applied on the wounded area by any spraying apparatus. The said composition may also contain callus forming agent and insecticide of prolonged effect.

Spraying with an 5 % solution of the composition according to the invention provides an effective protection. In case of aqueous sol 500 to 800 1/ha is efficient to apply. The application may be accompli ed by means of sprayer provided with spraying gun or other conventio way. During treatment the spray should be directed to the pruning surface .

In certain cases /e . g. at strong Eutypa infection of vine / also the active material per se , without dilution with water can be sprayed .

Another mode of use of the compositions is the dressing. For this purpose the active ingredient should preferably be used in

5-10 % aqueous solution with casein as preferred auxiliary on cereals , corn and onion. The use of casein is not absolutely necessary.

In case of tuber crops the time of dressing is 1 to 10 minutes . Cereals may be treated in conventional dressing apparatuses. For this purpose , emulsions of higher concentration /e . g. 40 to

GO % by weight/can also be used. The addition of indicator /red/ is preferred to the dressing emulsion .

The most effective protection is provided by the so-called "directed spraying" . For this purpose both self-propelled and trailed sprayers can be applied.

In the dormancy period after regeneration the composition of the invention should be diluted at +5 C to 5 % and sprayed by gun on the sawn or cut wound surface . This mode of treatment requires 400 to 600 ha/1 of spray solution . On infected apple trees the aqueous composition according to the invention may be applied in a dilution of 15 or in case of stronger infection 20 %. The application can be performed by any appropriate sprayer, using 500 to 800 ml of aqueous solution.

If the trunk or flowers of the tree or the cordon part of vine were sprayed in the fall or early winter /November and December the regular spring spraying may be eliminated.

It has been proved that the composition according to the invention penetrates as deep as 20 to 30 mm into the living tissues and kills the nymphs and grubs of bark- and phloem -de stroying insects as well as the spores and mycelia of the parasitic fungi therein without causing any damage to the plant.

As comparison, the biolog ical effects of the single com¬ ponents of the composition according to the invention have also be determined. It has been found that none of the basic active mate rial - hydroquinone system, the methyl methacrylate -hydroquionone system and the basic active material -methyl methacrylate system showed an effect comparable with that of the compositions according to the invention .

When omitting the hydroquiirone , the basic active material should have been kept suspended in the fluid monomer by continuous stirring in order to avoid sedimentation and discoloration. The thermal treatment of the basic active mate rial -hydroquinone system could only be performed in the presence of a solvent. For example , thermal treat¬ ment of Benomyl and hydroquinone in the presence of toluene yielded a mixture the biological activity of which did not exceed that of the basic active material.

Best Mode of Carrying out the Invention

The process according to the invention is illustrated by the following examples .

Example 1 1 part by weight of Chinalphos , 1 part by weight of Deltame followed by 1 part by weight of methyl methacrylate , 3 parts by weight of hydroquinone and 3 parts by weight of Benomyl were fed into a reactor provided with a stirrer, heated up to 110 °C and then cooled. Lutazol AT 25 emulsifier /tallow fatty alcohol ester, 25 EtO/ follow- ed by wetting agent containing 0,01 % fluorocarboxylic acid /Likovet,

Hoechst/ are added and the mixture was stirred , thus obtaining 9 kg of fluid dark brown product which can be filtered, if desired.

The solution thus obtained was sprayed on fruit trees , especially apple in an aqueous dilution of 0, 5 to 1 %. The composition can effectively be used against vegetative or parasitic fungal diseases and insects. The composition controlls powdery mildew , peronospora,

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stubbing fungi, clearwing moths , louses and mites.

The same solution was applied without dilution on cordon cultivation vine in spring or fall by the aid of a special spraying appara tus or brush. It has been established that after treatment the cordons infected with Eutypa and Cytospora cincta showed an intensive sprout¬ ing and leafing as a sign of destruction of the pests . When placing a tissue sample taken from vine cordon tissue killed by Eutypa on growth medium, no growth of Eutypa and Cytospora cincta could be observed after 7 to 8 days . As a result of treatment, the larvae and eggs of clearwing moths, grape-berry moths and mites situated beneath the bar were killed. The tissues which remained intact before the treatment thickened by midsummer and the leaves on the cordon wall were also normal.

Example 2 Following the procedure of Example 1 , 2 parts of methyl methacrylate, 2 parts of Benomyl, 2 parts of hydroquinone and 0,5 part of Chinalphos were heated to 110 C under stirring. To the mixture

2 to 3 % of polyvinyl butyrate coloured by 0,5 % of sudan red were adde

After cooling the wetting agent according to Example 1 was added and the mixture was diluted with 5 % of terpentine calculated on the total amount of the solution. The viscosity was adjusted to 6 * 0 to 70 cP by the addition of methyl methacrylate .

The solution thus obtained was applied to the surface of apple trees infected with clearwing and the fungi Cytospora cincta and Eutypa or Sphaeropsis malorum, resp. , or to the bark of stone-fruit trees strongly infected with Enarmonia formoson, using a special spray The surface of wounds was opened 20 minutes after treatment and dead larvae and nymphs were found.

Samples were taken from the tissues destructed by the parasitic fungi, placed on the surface of a medium, incubated and obser

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on the eighth day. No fungal growth could be observed on the medium. The cocons of the wooly aphids , scales and leaf -minor flies were killed and the eggs were dried. The same are resistant against regular plant protecting agents due to a wax layer on their surface which prevents the contact with the eggs. It has also been found that the adhesive layer binding the fibrine filaments which build up the cocon, was dissolved, thus destroying the structure .

Example 3

The product of Example 2 was completed with 4 % by weight of quinine hydrochloride or quinine sulfate . The solution thus obtained was sprayed on the bark of young trees at the end of October or early November. It was found that the barks were not damaged by wild animals especially rabbits during winter. The application on vine cordon, beside the effects as in Example 1 , also prevented the damages of frost.

Example 4

1 part of Benomyl , 1 part of Chinalphos , 1 part of D eltame 1 ,5 parts of hydroquinone and 3 parts of methyl methacrylate were stir in a reactor at 105 C for one hour.

The mixture was allowed to cool to room temperature and Lutazol AT 25 emulsifier and 0, 01 % of Likovet wetting agent were mixed thereto. If desired, the dark brown solution was filtered. 1 to 2 % of quinine hydrochloride was dissolved in the above system.

The 0,5 to 1 % aqueous dilution of the above solution was applied on corn, young pine and budding vine . No damages caused by wild animals could be observed. The treatment also resulted in the destruction of insect eggs beneath the bark.

Example 5

The mixture of 75 g of Triadimephon, 100 g of Folpet, 100

of hydroquinone , 3000 g of methyl methacrylate , 80 g of Chloropropylate , 100 g of Chinalphos and 100 g of Deltametrine was heated at 110 °C for 1/2 hour. After cooling, 1 to 5 % of Lutazol or lauryl sulfate emul¬ sifier and 0, 01 % of Likovet wetting agent were added. To the brownish solution 0,4 % of trace element composition, e. g. "Wuxal" was added as a 1 % solution.

0,4 to 0, 5 % aqueous dilution was prepared and applied on the surface of infected vine by conventional methods. After a few days the localization of powdery mildew and peronospora on the surface of leaves could be observed. In case of no infection at the time of treatment, a total protection was provided. The same effect could be observed against blue mold rot and insect pests .

Example 6

The active substance of Example 5 was prepared and after cooling, 20 g of B , vitamin and 1 mg of alfa-naphtyl acetic acid were added. Before diluting with water , 0, 01 % of trace element composi ion was added / e . g. Mikom.it/ .

After spraying the composition on cordon leaf system the leaves turned to deep green. The leaf analysis showed that due to the increased trace element, especially iron and manganese content, the assimilation activity was enhanced, as the microelements penetrate in the deeper tissue layers. The increase of ion intake was also observ¬ ed.

It is well-known that 80 to 90 % of vine possess mechanically or biologically injured tissues. On the effect of cellulose degrading enzimes being present in the tissues which are activated by the injuries of the tissue , the viscosity of fluids increases becoming unable to keep the metal ions in solution. Thus , the ions needed for vegetation cannot be supplied by intake from the soil. The treatment according to this example ensures intake of fluids and ions in the deeper tissue layers.

Example 7

The preparation and components of the active material wer identical with those of Example 6. After cooling, when adding the emulsifier and wetting agent, 5 mg of gibberellic acid, 5 mg of beta-indolyl butyric acid and 10 mg of potassium hydrogen carbonate were also mixed to the solution. The composition was used as 0,5 % aqueous dilution after mixing with 0,4 % of trace element mixtu

By spraying 10 to 14 days before vine blooming the number of flowers increased by 30 to 40 %. Treatment with the same solution after blooming increased the number of knots by 70 to 80 %.

The same treatment 14 days after blooming resulted as follows :

- the ripening period shortened by 20 days , - the sugar content increased by 3 to 4 %,

- the amount of grains decreased by 25 %.

The use of composition provided a permanent protection against peronospora, powdery mildew, blue mold rot as well as grap moths and mites .

Example 8

100 parts of methyl methacrylate , 20 parts of hydroquinone 1 part of Chinalphos , 1 part of Phormothion, 1 part of Deltametrin and 1 part of Chloropropylate were heated at 105 °C for one hour and 40 parts of ground oil shale was added /particle size 10 microns then cooled and mixed with 5 to 6 % of emulsifier /24 EtO/ and 0,01 of wetting agent /Likovet/.

The solution was diluted to a concentration of 1 % and spra on apple trees by conventional apparatus between July and Septembe

least 3 times. \

It was found that the calcium and magnesium content of apple increased, the structure of the fruits was harder and the storage period could be extended by 3 to 4 months . The fruits were free of insects and fungi.

Example 9

10 parts of methyl methacrylate, 2 parts of Triadimephon, 2 parts of hydroquinone , 4 parts of Permetrine , 1 part of etrame trine 5 parts of Benomyl , 1 part of Chloropropylate and 10 parts of Chinalph were heated at 110 C and cooled. 5 % of known emulsifier /Lutazol

AT 25 or alurin sulfate / and 0, 01 % of Likovet wetting agent were added .

1 to 1 ,5 % aqueous dilution of the mixture was applied on potato leaves by a 200 1/h sprayer. The treatment controlled the Phytosphora infection which is surprising as the Benomyl alone does not show the same effect. The potato leaves turned deep green.

Example 10

To the active material of Example 9 Baysilon PL silicon emulsifier was added and the mixture was diluted with water to 1 to 2 prior to spraying. Due to the silicon film formed on the surface of pota lea es, the Colorado beetle , which is frequently landing on potato plants and punctures the leaf surface before destruction, cannot depos the virus on the leaf. '

Example 11 Comparative experiment

The mixture of Example 1 was prepared but the heat trans

was omitted.

From the mixture completed with emulsifier and wetting agent, 0,5 and 1 % aqueous solutions were prepared. The composition thus obtained was sprayed on fruit trees against vegetative fungal diseases and insect pests . The growth of powdery mildew and χ)eronospo and scobbing could be observed on the foliage surface . Placing " scrapin from the trunk and branch on growth medium and treating as in the prece ing Examples, growth of parasitic fungi could be observed after 3 days .

The spray killed only 20 % of insects and 5 % of mites . Repeating the spraying after two weeks with the same composition, contr of powdery mildew was observed , growth of peronospora and parasitic fungi, however , remained unchanged. 10 to 15 % of the insects were killed.

Example 12 Comparative experiment

The process of Example 4 was repeated but without energy transmission. 0,4 to 0,5 % solution was prepared from the mixture and sprayed on the surface of vine -leaves . The growth of powdery mildew was inhibited but peronospora and blue mold rot injuries remained un- effected. 30 to 40 % of mites become paralysed but recovered in a few hours . 20 % destruction of grape-berry moths was observed.

Example 13

Comparative experiment

The process of Example 1 was repeated but without heating the solution. The material was sprayed on the cordon surface before budding and sample s were taken from the Eutypa-infected dead tissues which were placed on growth medium. After 48 hours intensive growth of Eutypa and Cytospora cyncta was observed.

Formation of malformed and strongly chlorophyll -defective leaves were also observed which were not regenerated. No effect on Eutypa could be detected.

Example 14 Dressing

To the mixture of Example 6 , 3 % of casein or ethyl acetate were added. The material was diluted to 15 % and evenly applied on the surface of wheat or corn grain in seed-dressor. 1 to 2 days after sowing the grains were sprouting and in 2 to 3 days the sprouts emerged from the soil. Sprouting of corn started at 5 to 6 C soil temperature and the sprouts emerged in a f ew days .

Carrying out the dressing with the same mixture which had been prepared by omitting the energy transmission, sprouting and emergi was delayed by at least 8 to 10 days .

Example 15

The process of Example 14 was repeated but adding 0, 2 % of lindane and leaving out the casein and acetates . The seed-grains were dressed in a fluidization mixer with the above solution.

The treated cereal grains were sprouting in 1 to 2 days and emerged after 3 to 4 days . The plants were removed after one month and proved to have a rich root in contrary to the plants emerged from seeds having been dressed by conventional methods. The cereals dresse and sown by this way grew green earlier and were more drought- resistant.

Example 16

The mixture of 15 parts of methyl methacrylate , 2 parts of hydroquinone , 5 parts of quinine hydrochloride , 1 part of Chinalphos ,

1 part of Deltametrin and 2 parts of Benomyl was heated at 110 °C for one hour and then stirred to a homogenous mixture . The 2 % aqueous mixture was sprayed on pine , aspen and oak. It was observed that the deers did not nibble off the top of pines , the fungi occuri g on the infected aspen and oak surfaces were localized , and, depending on the amount of the spray applied, the insects were killed , in some cases even in a depth of 2 to 3 mm.

Example 17

The mixture of 20 parts of methyl methacrylate , 2 parts of hydroquinone , 5 parts of Benomyl, 1 part of Captan, 1 part of

Deltametrine and 0,2 part of beta-indolyl butyric acid was heated at 105 C for one hour and stirred to a homogeneous mixture with known emulsifiers and wetting agents. The mixture was sprayed on alfalfa and sunflower in a dilution of 0, 3 to 2 %. The mixture provided a protection against leaf mildew of alfalfa and lodging of sunflower. By regular spraying, head rotting of sunflower could be eliminated. The wounds caused by aphids recovered without infection, the aphids them¬ selves were killed.

Example 18 The mixture of 18 parts of methyl methacrylate , 6 parts of Benomyl, 2 parts of Thiadimephon , 2 parts of hydroquinone , 1 part of alfa-naphtyl ace tic acid and 0,5 parts of beta-indolyl butyric acid was heated at 110 C for one hour , then cooled and mixed with emulsifier and wetting agents to homogeneous material, which was diluted to a concentration of 0,4 to 1 %.

At the end of September or in October, when spraying along with the top-dressing of wheat, winter barley and rye , the mass of roots increased, at least by 50 % compared with the controls. The number of

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leaves and chlorophyll content increased as well. As control, the basic active materials were used.

Example 19

In a reactor provided with a stirrer, 15 parts of methyl methacrylate, 3 parts of Benomyl, 1 part of Captan, 1 part of Folpet,

2 parts of Methidathion and 1 part of Deltametrine were placed. The stirring was accomplished with nitrogen gas. In the reactor double- walled quartz sound enclosing a 3400 to 3900 A quartz bulb was place The quartz bulb was switched on and the solution was stirred by nitro stream and cooled for 1/2 hour.

The composition can be used for dressing corn, wheat and alfalfa grains . After dressing the grains should simply be dried and t conventional covering with casein may be eliminated. The starch in the grain is bound to the composition through the OH -groups, thus providing protection against soil infections.

Example 20

The mixture of 20 parts of methyl methacrylate , 5 pa&s of Captafol, 3 parts of Benomyl, 1 part of Thiadimephon, 1 part of Deltametrine, 5 parts of Chinalphos and 2 parts of hydroquinone was stirred with hydrogen gas. The reactor was cooled and exposed to

4 MHz laser rays for 30 minutes. After 30 minutes the irradiation wa stopped and tfe mixture was cooled.

The mixture was dilited to a concentration of 0, 1 to 1 % and sprayed against apple scobbing, fungal diseases of potato, leaf- blight and potato -rot with excellent results.

Example 21

The mixture of 15 parts of methyl methacrylate , 1 part of

beta-indolyl butyric acid, 1 part of gibberellic acid, 2 parts of hydroquinone , 3 parts of Chinalphos , 1 part of Deltametrine and 5 parts of oil shale was heated at 105 °C for 1 /2 hour . After cooling to 70 °C a blend of wax and paraffin made at 70 C was mixed t hereto and /or a 20 % mixture was formed with vulcanizing silicon rubber. Before tubing, a known organic thin catalyst was added to the silicon rubber and sealed. The composition may be used at vine budding and grafting of fruit trees for covering the wounded or grafting surfaces , and eliminates the fungal infecftions on the reproductive material.