HU203927B - Process for producing fungicide preparation suitable for treating ligneous plants - Google Patents

Abstract

The invention relates to a composition for treatment of arborescent vegetation against fungal diseases. According to the invention also a process is provided for preparing the said compositions, characterized by contacting at least one fungicidal active compound with alkyl methacrylate in the presence of a cross-linking inhibitor by energy transmission and adding to the active material thus obtained a resin and/or wax. A further object of the invention is the use of the above compositions for controlling and preventing fungal diseases by the treatment with the said composition.

Description

The present invention relates to a process for the preparation of a fungicidal composition for the treatment of woody plants comprising the fungicidal active ingredient incorporated in a matrix of cross-linked alkyl methacrylate. The fungicidal active ingredient is incorporated into the matrix by energy crosslinking the C 1-6 alkyl methacrylate in the presence of one or more fungicidal agents and a cross-linking inhibitor, preferably hydroquinone.

Fungal diseases, which destroy the bark, bark and cambium of trees, are widespread in temperate trees on woody plants, especially ornamental trees and fruit crops; pathogens often also penetrate xylem. Diseases cause partial or complete destruction of trees. Diseases are widespread worldwide and cause economic damage to varying degrees depending on the country and the climatic conditions. So far, no adequate chemical control mechanism for diseases has been developed. Only limited and preventive protection can be achieved with the wound treatment agents available. In the case of an infection, treatment will only temporarily limit the spread of pathogens and recurrence of the disease should be anticipated.

Similarly, parasitic fungi also carry significant destruction in cordon cultivated vineyards.

Different factors in the bark of trees can cause injuries. These include frostbite or frost due to frost, sunburn crusting, snow pressure, cultivation equipment, shaker branching or open wounds, wild chewing, wounds caused by insects living in the deep tissue of the tree, and open wounds caused by pruning. This is compounded by cancerous wounds on the surface of trees caused by various fungi.

Through the "gates" opened above, parasitic fungi can penetrate the plant and cause serious disease.

The natural defense of the plant - biochemical and histological changes on the wound surface - takes place rapidly during periods of intensive growth and the infection stops. However, during the dormancy of the plant, the defense process is hardly or not carried out. Some of the fungi on the wound surfaces and the spores can even become infected at 0 ° C.

A variety of pesticides are available against various pests, but they can only be absorbed through the leaf or root when applied to the woody stalk and can only provide surface protection as they cannot penetrate the woody stalk.

Thus, it is known, for example, that a systemic fungicide known as benomyl has been tested against various pathogenic fungi, in particular Sytospora leucostoma, which causes Cytospora cancer in peaches. Only if the treatment was applied prior to infection was the pathogen fungicide achieved; they could not stop the existing infection, the plant could not be cured. This is because only surface protection was provided, and the agent did not penetrate through the crust and bark (Plant Disease Reporter 60 (1976) 477479). Studies with radioactive material of the American sylphane (Ulmus americana) have also shown that both penetration and translocation of benomyl are low (Chemical Central Slot, Ins. Ottawa Canada, Information Report CC-X47,1972).

No. 12281206. Federal Publication Publication in the Federal Republic of Germany discloses a coating agent for the treatment of injured trees comprising 375 parts of polyvinyl propionate and 1 part of a fungicidal agent. The composition is prepared by simply mixing the components and there is no mention that they can achieve any effect other than surface wound treatment.

No. 7,479,854. According to Japanese Patent Application, 0.5 parts by weight of polyethylene, 10 parts by weight of paraffin oil, 80 parts by weight of butene / isobutene copolymer, 5 parts by weight of vinyl acetate, 0.002 parts by weight of beta-naphthalic acid, 0.115 parts by weight of 8-hydroxyquinoline sulphate are used to prevent infection. a composition containing by weight ethyl acetate and 2 parts by weight turpentine oil tar. The composition is prepared by admixing the crosslinked polymer and other excipients with the fungicidal active ingredient.

No. 3044499. The invention is based on the discovery that when chlorophyll, carotene or carotenoid is added to known stool treatment compositions, the scarring can be accelerated.

N. Z. J. Agr. Gap. 1971, 14 (2), 526-34. The addition of 1% by weight of captafol and 1% by weight of HgO to the emulsion of the already crosslinked methyl methacrylate / octyl acrylate copolymer results in a good fungicidal and antibacterial but non phytotoxic formulation.

A common feature of known polymeric formulations is that the fungicidal active ingredient is mixed with an already crosslinked polymeric carrier and the polymer serves only to form a film on the surface of the fascia, which serves to prevent subsequent fungal infection. Another feature is that they are only suitable for killing fungi on the surface of the wound, they are preventive, they are not suitable for stopping the infection already inside the tree.

The aim of the present invention has therefore been to find a composition which is useful not only for surface wound treatment but also for controlling fungal pests in the bark and wood tissue of woody plants. The wound treatment composition is required to have a non-phytotoxic, broad-spectrum and long-lasting fungicidal action, to provide a lasting protective effect and to have a curative effect.

Surprisingly, it has been found that the above requirements can be met by a composition comprising the fungicidal active ingredient incorporated in a matrix of C 1 -C 6 alkyl methacrylate. The fungicidal active ingredient is incorporated into the matrix such that 0.9-10 parts by weight of C 1-6 alkyl methacrylate monomer contains 1 part by weight of one or more fungicidal agents and 0.1-5 parts by weight of a cross-linking inhibitor, preferably hydroquinone. -21

In the presence of HU 203 927 Β, it is crosslinked by energy communication. If desired, the material thus obtained is mixed with one or more solid carriers, preferably polyurethane resin, alkyd resin, paraffin, beeswax, aluminum pigment, titanium dioxide, silica, cobalt naphthenate and / or liquid carrier, preferably benzene, .

Systemic and non-systemic fungicidal agents can be used as the fungicidal agent for the preparation of the active compound of the present invention. The penetration of the fungicidal agent through the bark and bark tissue is ensured by the fact that when the C 1 -C 6 alkyl methacrylate is cross-linked in the presence of an inhibitor, the fungicidal agent is incorporated into the alkyl methacrylate molecular lattice and is able to penetrate the wood tissue. . Therefore, the quality of the fungicidal agent in the composition of the present invention is not determinable, it can be practically varied according to the disease to be treated, the fruit tree to be applied, the extent, the progression of the disease, etc.

Fungicides include, for example, one or more benzimidazole or triazole derivatives, fungicides containing copper and / or sulfur, cyanoacetic acid derivatives.

Preferably, for example, methyl (1-butylcarbamoyl) -2-benzimidazolecarbamate (benomyl), 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) - can be used. 2-butanone (triadimephone), 1-2 (-2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl-1H-1,2,4-triazole, beta (4-chloro) (phenoxy) -alpha-1,1-dimethyl-1 H -1,2,4-triazole-1-ethanol, 2,3-dicarbonitrile-1,4-dithio-anthraquinone, N 4 '- [1,4- piperazinyl bis (2,2,2-trichloroethylidene)] bis (foimamide) (triforine), copperamine (product obtained by reaction of 1 mole of copper sulfate with 1 mole of triethylamine), dimethyl (1,2-phenylene) bis (iminocarbonylthionyl) bis (carbamate) (topsin methyl).

Preferred inhibitors are hydroquinone, hydroquinone derivative, ascorbic acid, phenol phenol derivatives, hydroquinone being the most preferred. In addition to preventing unwanted polymerization of alkyl methacrylate, the inhibitors also provide some degree of bacteriostatic activity in the agent.

In preparing the active ingredient, the alkyl methacrylate is crosslinked in the presence of the fungicidal agent and the inhibitor. Preferably, 0.9 to 10 parts by weight of liquid alkyl methacrylate monomer and 0.8 to 10 parts by weight of inhibitor are used, based on 1 part by weight of the fungicidal agent.

The spatial crosslinking of the alkyl methacrylate is conveniently accomplished by energy transfer.

The energy transfer may be effected by heat treatment, ultraviolet or laser irradiation, preferably while stirring.

When the energy communication is accomplished by heat communication, it is preferable to mix the fungicidal agent, the alkyl methacrylate and the inhibitor, and then heat it to 100-130 ° C. The treatment can be continued for 0.5-3 hours.

Alternatively, the fungicidal agent, the alkyl methacrylate and the mixture of the inhibitor may be subjected to ultraviolet irradiation for 5 to 60 minutes at 10 to 20 ° C. preferably under cooling. Erié for the purpose 30005 5000 A quartz probe with a quartz burner operating in the range is placed in the reaction mixture in the reactor. The stirring in this case is carried out with an inert gas, preferably nitrogen or carbon dioxide. When working without cooling, approx. The reaction temperature rises to 80 ° C.

Alternatively, the fungicidal agent, a mixture of alkyl methacrylate and an inhibitor, is treated with laser radiation. Thus, for example, in a photochemical reactor, under vigorous cooling of water, with stirring with nitrogen, an argon-in laser of 488 nm (nanometer) is used, and at 1 W, the reaction takes place within 2-3 hours. When using 4 W equipment (6 laser lines enter the reaction area together), the reaction time is reduced to 30-40 minutes. This reaction routine avoids the need for thermal energy for the reaction and high control over the process

The active ingredient of the invention is used in admixture with one or more solid and / or liquid carriers in agricultural practice.

Suitable solid carriers are natural or artificial resins, waxes, pigments, pigment-containing agents, mica and other carriers conventionally used in agriculture.

Suitable liquid carriers are, for example, benzene, xylene, toluene, petroleum, paraffin oil butyl acetate, higher alcohols and the like. It can be used.

A variety of synthetic resins can be used as resins, such as alkyd, epoxy, styrene, silicone and / or polyurethane resins. Tar waxes include paraffin waxes (Canadian balsam, beeswax, Kamauba wax). Natural resins (shellac) may also be used.

The resin may be mixed with the composition in cold or warm amounts of 50-1001% by weight of the other materials. Alternatively, the resin may be dissolved in a suitable organic solvent prior to cooling with the material obtained from the inhibitor, the methacrylic acid alkyl ester and the starting material.

The resins are preferably used in a 40-70% solvent solution.

Preferably, a fascia treatment resin is prepared that contains 50-801% resin.

The composition can also be applied in a variety of forms, including a dense paste, a dense liquid solution or a spray.

When applied in the form of a paste or a dense liquid, a pigment or pigment-containing agent is preferably added as an additive, particularly to prevent ultraviolet radiation. such additives may be metallic pigments such as aluminum, bronze, copper alloys, manganese, etc. There may also be various oxides such as titanium dioxide, aluminum-31

It is also possible to apply mica, for example aluminum phosphide, kaldum phosphido. The composition should be applied in a thickness of 10 μm to 2 mm on the surface to be treated. 5

The wound treatment composition of the present invention protects against various infectious fungal diseases for 2-3 years and thus prevents secondary colonization of, for example, rotting fungi.

It also protects against a whole host of fungal species that attack the bark layer from the inside during infection

The effect of the composition of the present invention was investigated on various fungal diseases. These include 15:

- Cytospora cincta branch damage and death on peaches, apricots, cherries, cherries;

- cancer of pear and apple trees caused by Phacidiella discolor; 20

- black cancer of Sphaeropsis malorum in apple and pear trees;

- Nectria galligena is also a cancer of pear and apple trees.

Because pathogenic fungi are wound parasites, wound healing and professional use of wound healing agents play an important role in controlling these diseases.

The in vitro laboratory testing of the formulations was carried out on petri dish dextrose agar medium in petri dishes. The medium was inoculated at three points and incubated for 2-5 days depending on the growth power of each fungal species. After incubation, 0.1 mL of the test drug was added to the wells in the middle of the plates. The plates were further incubated until the fungicidal effect of the untreated controls was completely overgrown with the plate.

Table I illustrates the effect of the product of Example 1 (MBH) on various fungi. It can be seen that MBH showed complete inhibition in all five fungal species tested, and the fungus lost its viability

By way of comparison, the biological effect of the individual components of the benomylmethyl methacrylate hydroquinone alkyd resin composition alone was investigated. It has been found that the benomyl hydroquinone system, the methyl methacrylate hydroquinone system, the benomyl methyl methacrylate system, and the benomyl resin system do not produce the effect of the present invention. When the hydroquinone is omitted, the benomyl suspended in the liquid monomer is stable. it had to be stirred in the air, settling to the bottom of the vessel and gradually discolored The heat treatment of the benomyl hydroquinone system was possible only in the presence of a solvent. Heat treatment at 110 ° C for 48 hours in the presence of toluene gave a mixture which was biologically equivalent to benomyl, i.e. only had a surface effect of 60 (which may be due to the antibacterial activity of hydroquinone, also only surface).

Examples of effects

Example I

The effects of the compositions of the present invention are

, we examined the following fungi: Cytospora cincta őszibarackról Sphaeropsis malorum apple tree Phomopsis mali apple tree Phacidiella discolor pear tree Chondrostereum purpureum apple tree Eutypa armeniacae kajsziról Pesicula malicorticis apple tree.

In addition to showing the effects, in some cases the commercially available Santar SM faseb treatment preparation (Active ingredient: cis-N - [(1,1,2,2-tetrachloroethyl) thio] -4-cyclohexene-1) is shown in parallel. 2-dicarboximide mixed with a crosslinked polymeric carrier.)

Table 7

mushroom Untreated control Product of Example 1 Santar SM Product of Example 7 Cytospora cincta 0 TG 20% TG Phomopsis mali 0 TG 5% TG Sphaeropsis malorum 0 TG 20% TG Stereum purpureum 0 TG 20% 0 Phacidiella discolor 0 TG TG TG

TG = total inhibition; % of the fungus has lost its viability; beyond the inhibition zone, fungal colonies maintain their viability,

- no inhibition, fungal colonies completely overgrown with petri dish,

EG »strong inhibition.

7 /. example

Table 11

mushroom untreated control Product of Example 3 Cryptosporiopsis corticola 0 TG Cryptosporiopsis malicorticis 0 TG Diplodia sp. 0 SKY Eutypa armeniacae 0 TG Coryneum microstictum 0 TG Libertella blepharis 0 TG Stereum purpureum 0 SKY

HU 203 927 Β

HL example

Field experiments were conducted at the Plant Protection Research Institute in Nagykovac to test the compositions of the present invention.

On peach trees, Cytospora cincta fungus ulcer wounds were cleaned with a knife to intact tissue, and dense liquid formulations were applied by brush to the untreated surface. For comparison, Santar SM is commercially available. 10

The results of the field tests are as follows:

the)

With the product of Example 1

At 8 months after drug treatment, tissue pieces were transferred from the infected and treated tissue sections to sterile PDA medium. Thus, it was confirmed by isolation that no fungal mycelium remained in the xylem, which confirms the curative effect of the agent. It did not inhibit callus formation on peaches. It has an excellent fungicidal effect. 20

b)

Example 5

The agent has sufficient fungicidal activity when tested in accordance with (a). The re-isolation of the tissue under the treated surface was negative, meaning that the 25 pathogens could not be detected after 8 months, confirming the curative effect. It forms an excellent surface: half a year after the treatment, the surface formed by the drug did not change, no cracks appeared.

Under pressure of the resulting callus, the resulting layer is permeable and thus does not inhibit its growth.

c)

Santar SM does not form a durable surface. Dehydration of the cleaned surface (xylem) creates deep cracks which provide another opportunity for fungi to penetrate. After 8 months of treatment, Cytospora can be isolated from xylem in viable condition.

d)

The inoculum wax is conditionally useful, it often detaches from the treated surface 40, has no fungicidal effect, and in fact, under the surface formed by the wax, the mycelium of the Cytospora cincta fungus accumulates in large quantities.

ARC. example

Field experiment: Cytospora cincta fungus was infected with peaches at 100 points. Two weeks after infection, the composition of Example 8 was applied as an aqueous solution at 30 infected sites by spraying the contents of the bottle twice, three times, in 50 sprays, to form a uniform coating. We attempted to isolate the pathogen 1 week after treatment. The result is shown in the table below: 55 isolates treated 0 controls 100%

In both cases, fungal isolation was performed on 10-10 samples. 60

Example V

Field study of the Plant Protection Research Institute:

The penetration of our product into wood tissue was investigated in vivo. The study was carried out on the cut branches of peaches planted 4-5 years ago. We applied it to the freshly sawn surface:

(a) the active ingredient benomyl + methyl methacrylate + hydroquinone according to Example 1,

b) The composition of Example 1, b) After an hour, the treated surface was peeled off at a thickness of 5 mm, and several slices of 5 mm thickness were cut off below the branch. These discs were placed on PDA medium inoculated with conidia of Penicillium cyclopium after surface flaming. After incubation at 26 ° C for 48 hours, the plates were evaluated. (See Table ΙΠ)

1. In the case of Santar SM, no inhibitory effect (inhibition zone) was observed on the plates.

2. a clear inhibition zone of up to 15 mm was observed for the preparation,

3. there was a definite zone of inhibition up to 30 mm for the active substance.

With this bioassay, it was demonstrated that the fungicidal agent of the invention penetrated into the woody tissue elements from the treated surface.

Details of our procedure are given in the Examples.

Table HL

Penetration mm 5 10 IS 20 25 30 Resin preparation (Formulated product of Example 1) + + + - - - Active substance (Example 1) + + + + + + Santar SM - - - - - -

Example 1

In a stirred reactor, 55 kg of methyl methacrylate and 20 kg of bydroquinone are mixed and 25 kg of benomyl is added. The reaction mixture was heated to 110 ° C and stirred at this temperature for 1 hour. The biphasic reaction mixture was cooled. 100 kg of product are obtained. This active ingredient is used as an active ingredient in the absence of additives in Annexes I and III. Table I.

The following resin is prepared:

100 kg of sunflower fatty acid, 40 kg of pentaerythritol, 55 kg of phthalic anhydride and 8 kg of xylene are weighed. Reflux at 220 ° C for 4 hours (acidity max. 25 mg KOH / g). Meanwhile, the resulting water was removed by azeotropic distillation. The reaction mixture was cooled to 150 ° C and 180 parts by weight of white spirit were added to make a solution. The viscosity of the product (in beaker 4) measured at 20 'C is 180200 sec. 383 kg of petrol solution are obtained.

HU 203 927 Β

Add the following additives to the above solution:

100 kg aluminum pigment (so-called "silver pigment") kg Aerosil-380 (finely divided silica) kg cobalt naphthenate

200 kg silicone varnish kg titanium dioxide.

The addition is carried out with vigorous stirring. The above homogenous mixture (total of 421 kg) is mixed with the substances obtained according to the first two paragraphs in the following proportions:

320 kg active ingredient

310 kg petrol resin solution

1051 kg of liquid product (active ingredient content: 30.471%) are obtained which can be directly applied to the treatment of trees by brush or spray.

Example 2

The procedure of Example 1 is followed except that the active ingredient is prepared from the following materials as in Example 1:

130kgbenomyl

150 kg of methyl methacylate monomer, kg of hydroquinone.

To the resulting product were added the additives given in Example 1. The product is suitable for the treatment of fascia. Active ingredient content: 201%.

Example 3

The following amounts of starting materials were used as in Example 1: Triadimefon Methyl Methacrylate Monomer Hydroquinone Petrol Resin Aluminum Pigment

Aerosil 380 cobalt naphthenate silicone varnish titanium dioxide

6.00% by weight

20.00% by weight

4.00% by weight

28.00% by weight 10.00% by weight 5.00% by weight 0.10% by weight 19.86% by weight 7.00% by weight

The resulting products can be used for the treatment of fascias: they have a preventive and curative effect against fungal infections such as powdery mildew.

Example 4

3 parts by weight of methyl methacrylate and 2 parts by weight of hydroquinone were charged into a K & T reactor and 3 parts by weight of benomyl were added with stirring. Stirring was carried out with nitrogen gas. The reactor is equipped with a double-walled cooled quartz probe with a quartz burner operating in the 3400-3900 Å range. The quartz burner was put into operation and the solution was stirred under a stream of nitrogen gas for half an hour. To the biphasic product, resin and additives as in Example 1 were added to give 821% active ingredient. The product can be used in the same manner as the product of Example 1.

Example 5

To the reflux condenser was added 1 part by weight of benomyl, 2 parts by weight of methyl methacrylate and 1 part by weight of hydroquinone. The mixture was stirred vigorously under a stream of nitrogen. The reactor is equipped with a quartz probe in which a quartz burner operating in the 3400-3900 Å range is commissioned. The quartz burner causes the temperature to rise to 80 ° C. After stirring for 10 minutes at reflux, the operation is stopped, the material is cooled, and 1.5 parts by weight of the resin of Example 1 are added. The product (active ingredient content: 72.7% w / w) can be used as a fungicide for treating wounds with curative and preventive effects as described in the section on efficacy.

Example 6

The fungicidal agent used is 1-2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl-1 H -1,2,4-triazole. Material 6 kg fungicide, 8 kg of methyl ME20 hydroxyethylmethacrylate monomer, and 6 kg of hydroquinone A mixture stirred reactor heated at 110 C for 1 hour at ^this, the mixture was cooled to 20 ° C to room temperature.

In another reactor, 11 kg of anhydrous butyl acetate25 are dissolved in 40 kg of polyisocyanate prepolymer ("desmodur E-21") and mixed under anhydrous nitrogen with 10 kg of aluminum pigment, 6 kg of titanium dioxide and 3 kg of finely divided silicon. ("Aerosil-380").

The mixture is added to the active ingredient prepared according to the first paragraph and then stirred until a homogeneous product is obtained. This requires 30 minutes at room temperature.

The resulting solution is bottled under carbon dioxide pressure. The active ingredient content of the preparation is 22.21%.

The products are excellent against curative and preventive effects against powdery mildew, Uncinula necator, Guignaidia bidwelli fungi. Excellent film-forming properties: durable, high strength. On treated wood, the protective layer remains unchanged for more than a year. It does not inhibit the growth of wood.

Example 7 Parts by weight of methyl methacrylate, 0.5 parts by weight of hydroquinone hyd45 and 2 parts by weight of benomyl. The system was stirred with hydrogen gas. The reactor was cooled and loaded with a 4 MHz infrared laser for 30 minutes. After 30 minutes, the reaction is stopped, the reaction mixture is cooled, and the ingredients of Example 1 are added in an amount of 10 parts by weight. The composition thus obtained contains 42.8% active ingredient. The resulting preparation is applied to the cleaned surface of the fascia: the tissue sample does not show any development of parasitic fungi on the medium.

Example 8

In a stirred reactor, 20 parts of methyl methacrylate, 2 parts of hydroquinone are mixed and 3 parts of beta-4-chlorophenoxy-alpha-1,1-dimethyl-1 H -1,2,4-triazole-1 -61 are added as a starting material.

Ethanol The mixture was heated at 110 ° C for 1 hour then cooled and a total of 1250 parts by weight of resin and excipients were added according to Example 6. The product obtained has an active ingredient content of 21% and can be applied by brush or spray to the cleaned wound surface. Durable, excellent facial treatment.

Example 9 Benomyl kg (65 kg), butyl methacrylate (65 kg) and hydroquinone (20 kg) were heated at 120 ° C for 1 hour. A solution of 0.5 kg Aerosil-380, 0.1 kg cobalt naphthenate, 20 kg methyl-based silicone varnish and 7.0 kg titanium dioxide was added. The product is homogenized. The active ingredient content of the 15 products is 31%.

The product is advantageous during the vegetation period in case of cancer of cherries or peaches.

Example 70 1-2 kg of 2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl-1H-1,2,4-triazole, 8 kg of methyl methacrylate monomer and The mixture was stirred at 110 ° C for 50 minutes. The mixture was cooled to room temperature. 25 The following products are made in separate containers:

10 kg of beeswax 10 kg of paraffin, 10 kg of aluminum pigment (paraffin coated), 0.5 kg of finely divided silica (Aerosil-320) are dissolved with gentle heating and stirring. The resulting mixture is added to the active ingredient prepared according to the first paragraph and the homogenized product is cooled. A pasty material is obtained as a product

The product can be used as inoculum wax for inoculation of fruit trees (apples, peaches, cherries), for protection of the inoculation or eye area during grape and rose analyzes. Kizaya is found in Eutypa armeniacae, respectively. Cytospora cincta fungus infections brought by the vaccine. Among the vaccines, there is no evidence of cancer at the injection site after 1 year. 40

Example 77

The fungicidal agent used is a mixture of 3 parts by weight of benomyl and 3 parts by weight of beta (4-chlorophenoxy) -alpha (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol. In the same manner as in Example 1.45, 4 parts by weight of methyl methacrylate and 23 parts by weight of hydroquinone are reacted with 15 parts by weight of an alkyd resin, 5 parts by weight of the compound of Example 1 and additive. 50

The product obtained is an excellent fungicidal agent for the treatment of fungi, which can be used for curative and preventive action against fungi such as Cytospora cincta, Stereum purpureum and Eutypa armeniacae, for example apricot. 55

Example 12 kg of 2,3-dicarbonitrile-1,4-dithio-anthraquinone, 11 kg of methyl methacrylate monomer and 6 kg of hydroquinone were heated at 110 ° C for 1 1/4 hours. kg resin and 7 kg additive. Active ingredient content: 44.41%. The product can be used as a preventive and curative agent against fungal infections on peach trees.

Example 13 A mixture of kg of triforine, 8 kg of methyl methacrylate and 6 kg of hydroquinone was heated at 110 ° C for 1 hour. The product was cooled and polyurethane resin dissolved in gasoline was added. After the addition of further excipients, it is used as a faseb treatment of apricot on the apricot tree with a preventive and curative effect against fungal infections.

Example 14 kg of methyl methacrylate monomer, 1 kg of hydroquinone, 5 kg of "copperamine" (1 mol of copper sulphate and 1 mol of triethylamine) and 1 kg of surface-treated sulfur. After stirring at 105 ° C for 1 hour, it is cooled and 28 kg of a solution of 60 parts of petrol and 40 parts of alkyd resin are added. After the addition of 35 kg of the additive according to Example 1, it can be used as a stool treatment.

Example 75 kg of topsin-methyl, 3 kg of methyl methacrylate, 1 kg of 1,2 (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl-1H1,2,4 -triazole, 2 kg of hydroquinone mixture was heated at 110 ° C for 1 h. Cooled and a solution of 7 kg (65 parts of gasoline and 35 parts of alkyd resin) was added. According to Example 1, an additional 30 kg of additive was added and stirred until a homogeneous mixture was obtained. Active ingredient content: 15.91%. The composition is filled into aerosol cans and 50 g of freon 11 and 50 g of freon 12 are added per 100 g under ingestion. The bottle is sealed, valveed and sprayed. Spray onto cleaned wound surface of trees after 8 months and show no growth of parasitic fungus on isolated tissue sample medium after 2-3 days.

Claims (8)

CLAIMS 1. A process for the preparation of a fungicidal composition for the treatment of woody plants comprising the step of curing with 0.910 parts by weight of a C 1-6 alkyl methacrylate monomer in the presence of 1 part by weight of one or more fungicides and 0.1-5 parts by weight. optionally in an inert gas atmosphere with stirring and then mixing the resulting material with one or more solid or liquid carriers, if desired. 2. The process of claim 1 wherein the inhibitor is hydroquinone. The method of claim 1, wherein the energy communication is accomplished by heat communication, ultraviolet or laser irradiation. The process according to claim 1, wherein the crosslinking is carried out under nitrogen or carbon dioxide. ' -7HU 203 927 Β The process according to claim 1, wherein the fungicidal agent is 1- 2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl-1H-1,2, 4-triazole, beta (4-chlorophenoxy) -alpha-1,1-dimethyl-1H-1,2,4-triazole-ethanol, 2,3-dicarbonitrile-1,4-dithio-anthraquinone, copperamine, methyl - (1-butylcarbamoyl) -2-benzimidazole carbamate, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, N, N '- [1,4-piperazinylbis (2,2,2-trichloroethylidene)] bis (formamide) and / or dimethyl (1,2-phenylene) bis (iminocarbonothionyl) bis (carbamate) ). 6. The process of claim 1 wherein the methyl methacrylate is methyl methacrylate. The process according to claim 1, wherein the solid support is polyurethane resin, alkyd resin, paraffin, beeswax, aluminum pigment, titanium dioxide, silica and / or cobalt naphthenate. 8. The process of claim 1 wherein the liquid barrel is gasoline, butyl acetate and / or water.