CS274279B2 - Fungicide - Google Patents

Abstract

The agent for treatment and/or prevention of diseases caused by fungi of tree vegetation on the base of resin, containing at least one fungicide selected from the group involving derivates of benzimidazole, triazine, piperazine, cyanoacetic acid, fungicides containing copper and/or sulphur and their mixtures. The agent further contains C1-4 alkyl methacrylate and hydroquinone. The ratio of the fungicidally active component to methacrylate to hydroquinone is 3 to 12 : 9 to 25 : 1 to 9. In relation to the amount of the mentioned components, the agent contains from 10 to 300 percent by weight of resin, selected from the group including alkyd, epoxy, styrene, silicon and/or poly-urethane resin and tar, and/or wax.

Description

The present invention relates to novel compositions for the treatment of plant diseases caused by parasitic fungi on plants that live on the bark and woody tissues of tree vegetation. Another object of the present invention is the preparation and use of novel plant protection products.

Certain fungal infections causing the destruction of bark, bast and cannabis are widespread in tree vegetation, mainly decorative and fruit trees of the temperate zone, these pathogens often penetrate the xylem. These infections can cause partial or total destruction. Infections can cause considerable economic damage. So far no adequate protection has been found. Available protection materials provide only limited or preventive protection. The treatment allows so much temporary control of the petogens and can be expected to re-establish the disease.

Similarly, parasitic fungi also cause palpable destruction of cordon vineyard cultivation.

Bark damage can be caused by different effects, such as skin damage caused by frost, sun bark wasting, snow breaks, ice, cultivation tools, vibrators, etc., open wounds, game animals, damaged plant insects or open wounds caused by pruning. These openings provide an easy way for insects and parasitic fungi to enter plants and thus cause serious infections *

In the intensive growth period, the natural lmunoeyetas of the plant rapidly activate by biochemical and hietological changes in the wound area and suppress the infection of es. However, during the rest period there is no defense response or very protective reaction, the fungal count appears on the wound surface and spores can cause infection 1 at 0 ° C.

It is also known that a large number of fungicides of different types are available, but these fungicides are effective only if they penetrate the leaves or roots or provide only surface protection.

For example, the eyetemic fungicide Benomyl has been tested against different pathogenic fungi, particularly Cytoepora leucoatorna, which is the cause of Cytoepora carcinoma in peach trees. Control was only possible if. If treatment was performed prior to infection. An infection that has already developed could not be reversed and the plant could not be cured. The reason for this is that ee achieves only surface protection and the composition cannot penetrate the bark of the bile (Pian Dieeaee Reporter 60, 477-479 (1976)). A radioactive study on the Elm (Ulmus americene) shows that both shoot penetration and tranalocations are low (Chemical Central Res, Inc, Ottawa, Canada, Information Report CC-X-47 (1972)) ·

The present invention does not help to provide a composition capable of controlling parasitic fungi living in the bark and woody tissues of tree vegetation and meets the following requirements:

- is not phytotoxic,

- provides a broad fungicidal action and an extended duration of action,

- form a durable protective layer which does not disintegrate and washes neither in the sun nor in the rain,

- besides the preventive effect it has the same therapeutic effect, it is able to penetrate the woody tissue through the bark and bast.

It has been found that a composition meeting the above requirements can be prepared by contacting one or more fungally active chemical compounds (parent drug) and an alkyl methacrylate in the presence of a compound or compounds inhibiting energy transfer and mixing the thus obtained product 8 with resin and / or wax in presence or absence of an organic solvent,

As fungally active compounds, eyetemic, non-enzymatic fungicides may be used. Penetration is achieved by treating the material obtained with the interaction and the alkyl methacrylate and inhibitor.

CS 274 279 B2

According to the invention, it is an agent for the treatment and / or prevention of diseases caused by fungi in the bark and woody tissue of a tree-based resinous vegetation and contains one or more fungicidally active compounds selected from benzimidazole, triazine, piperazine, cyanoacetic acid, / or sulfur and deer. The composition further comprises a C 1 -C 4 alkyl methacrylate, hydroquinone, wherein the ratio of the fungicidally active ingredient to the acrylates to the hydroquinone is from 3 to 12 to 9 to 25 to 9. comprises 10 to 300% by weight of a resin selected from the group consisting of alkyd, epoxy, styrene, silicone and / or polyurethane resins and tar, and / or wax;

Preferred fungicides are the following commercially available compounds: Methoxycarbamoyl benzimldazole, Benomyl, Captafol, Zlneb, Thiophanate-methyl, Procymidone, 2-n-octyl-n-isothiazolin-3-one, Cursate, copper oxychloride, Penarimol, Captan, Metidathion, 8 -oxychlnoline sulphate, Tripborne, Xprodion, Vinchlozolin and emes or mixtures thereof ·

Resins are, for example, synthetic resins, for example alkyd resins, epoxy resins, styrene, silicone and / or polyurethane resins and tar. Examples of wax are paraffin, natural waxes (Canadian balsam, beeswax, carnauba wax). Natural resins, such as whites, can also be used.

Preferred inhibitors of the invention may be hydroquinone and derivatives thereof, ascorbic acid, phenol and derivatives thereof. These compounds have a bacteriostatic effect in addition to the inhibitory effect of preventing undesired polymerization of alkyl methacrylate.

The energy transfer can be achieved, for example, by heat, ultraviolet radiation or laser radiation, preferably with stirring.

Since the energy transfer is effected by heat, the active ingredient, the alkyl methacrylate and the inhibitor are stirred and heated up to a temperature of 100 to 130 ° C. The treatment is preferably carried out for 0.5 to 3 hours.

According to another embodiment of the invention, the mixture of the alkyl methacrylate, the basic active ingredient and the inhibitor is treated with ultraviolet radiation for 5 to 60 minutes at a temperature of 10 to 20 ° C, preferably with cooling. To this end, the quartz probe provides a condenser and a quartz flask operating in the range of 300 to 500 nm ee to be ground into the reactor. In this case, the stirring is performed with an inert gas, preferably nitrogen or carbon dioxide. When working without cooling, the reaction temperature rose to 80 ° C *

According to another embodiment of the invention, the mixture of the alkyl methacrylate, the basic active ingredient and the inhibitor is treated by laser radiation. For example, ee operates in a photochemical reactor under vigorous cooling with water and nitrogen stirring, using 488 nm argon ions at a reactor power of 1 W located for 2 to 3 hours. Using a 4W apparatus (6 laser lines entering together into the reaction space), the reaction time was between 30 and 40 minutes. This embodiment of the reaction eliminates the need for thermal energy e the reaction ee can be safely controlled.

According to the invention, the ratio of the reactants is 0.9 to 10 parts by weight. % of liquid alkyl methacrylate monomer; inhibitor to 1 part by weight of the basic active ingredient.

The material so obtained is mixed with resins of different types to obtain a wound treatment resin according to the invention.

The resin is mixed to the composition in an amount of 50 to 100% by weight, based on the total amount of other materials, if desired, with heating. According to another embodiment of the invention, the resin is dissolved in a solvent and added to the material obtained by the reaction of the inhibitor, the alkyl methacrylate and the active ingredient base before cooling.

Suitable solvents for this purpose, depending on the type of resin, are gasoline, xylene, toluene, petroleum, paraffin oil, butyl acetate, higher alcohols and the like.

CS 274 279 B2

The concentration of these resin solutions is preferably 40 to 70% by weight. A preferred ren treatment resin comprises 50 to 80 wt. resin.

For example, the composition may be formulated into a paste, saline or aqueous solution (such as an epray) farm.

If necessary, additives, pigments or materials containing pigments may also be added to the composition. Such additives are, for example, indatene derivatives, which are then degraded when exposed to ultraviolet radiation.

In the case of a composition in the form of a paste or a viscous solution, preferably a pigment or pigment-containing material is added to the system, especially for protection against ultraviolet radiation. Such additives are, for example, metal pigments such as aluminum, bronze, copper, manganese alloys and the like. Other suitable pigments are oxides such as titanium dioxide, carbon dioxide, barium oxide or, finely divided silica, as well as mica such as aluminum, calcium and the like.

The wood treatment composition of the present invention may also contain other well known adjuvants.

The composition ae is applied to the surface by acting in a layer thickness of 10 µm to 2 mm.

The composition according to the invention provides protection against secondary infections caused by fungus for 2 to 3 years, so that, for example, secondary rot caused by fungi is prevented. It shows and not only protective, but also a therapeutic effect against a number of fungal strains that attack the bast from the inside.

The biological activity of the composition according to the invention has been tested against various roetlin diseases caused by fungi, inter alia:

- carcinoma caused by Cytoapora clnota and destruction of peach trees, apricots, cherries,

- carcinoma caused by Phacidialle diecolor on apple and pear,

black carcinoma caused by sphaeropsis malorum on apple and pear trees, and

- carcinoma caused by Nectrlna galligena on apple and pear.

When infectious fungi are fungi parasitic to the wound, wound treatment and the professional use of the treatment material play an important role in protection.

In 1n vivo laboratory tests, the compositions were tested on a potato dextrose medium in Potri. bowls. The o medium was inoculated with 3 spots and incubated for 3 to 5 days depending on the growth rate. After incubation aa in the center of each mist, it created an opening into which 0.1 ml of test material was dripped. The plates were then incubated until the treated control mice had grown completely. Evaluation of the fungicidal effect was performed by measuring the inhibition zones. Table 1 shows the efficacy of the product obtained according to Example 1 (MBH) on different fungi. The composition designated MBH exhibits a complete inhibitory effect against all fungi.

For comparison, they also determined the biological effects of the individual components of the composition, Benzyl, methyl methacrylate, hydroquinone, and alkyd resin. It has been found that none of the Bensmyl hydroquinone system, the methyl methacrylate hydroquinone system, and the Benomyl methyl methacrylate eyetem has an effect comparable to that of the invention.

When the hydroquinone was omitted, Benomyl was kept suspended in the liquid monomer by continuous stirring to avoid sedimentation or discoloration. The heat treatment of the Benomyl hydroquinone eyetem can only be carried out in the presence of a solvent. For example, heat treatment of Benomyl and hydroquinone in toluene at 110 ° C for 48 hours provides an ama whose biological effect does not exceed that of Benomyl, i.e., achieves only e surface activity.

The biological activity of the compositions of the invention was tested against the following fungi:

Mushroom

CS 274 279 B2 on the plant

Cytoepora cincta peach trees Sphaaropsis malorum apple tree Phomopois mail apple tree Phacldlalla diacolor pear Chondrootaraum purpuraum apple tree Eutypa armeniacae apricot Pazlcula mallcorticla Apple tree

also tested the biological effect of a commercially available SanPro composition against tar SM.

Example I Table I

Mushroom

Neoěatřená

Product

Santar SM

Product

control from the example 1 from example 7 CytO8pora cincta 0 ÚP 20% LO Phomopala had 0 ÚP 5% LO Sphaeropaia malorum 0 ÚP 20% LO Steraum purpuraum 0 , ÚP 20% 0 Phacidialla diacolor 0 ÚP ÚP ÚP Explanation: LO means complete suppression. % means partial suppression caused by the device and is expressed as and as percentage of desktop. Okolc and inhibitory zone the live fungus remains unchanged. 0 means no inhibitory effect, milk me streaky. Example II Table XI Mushroom Untreated product from example 3 Cryptoaporlopela corticola 0 0. Cryptosporiopsls malicorticis 0 ÚP Oiplodla ap. 0 Sl Eutypa armeniacae 0 ÚP Coryneum microstlctum 0 ÚP Llbertella blapharia 0 ÚP Staraum purpuraum 0 SI

Explanation: LO means complete suppression.

SI means strong inhibition.

CS 274 279 B2

Example 1X1

In order to determine the biological effect of the compounds of the invention, tests were carried out in the open.

Cancer-wounded apricot infestations infected with Cytospora cinta were cleaned in depth and even on healthy tissue and coated with a brush with compositions as a viscous liquid. Santar SM.

The following results were achieved:

(e) The product of Example 1

At eight months after treatment, tissue fragments obtained from infected and treated tissues were transferred to sterile PDA media. It has been found that no mycellum remains in the xylem, indicating a therapeutic effect. * No inhibition of the caving formation was determined. The product had an excellent fungicidal effect.

(b) The product of Example 6

According to the test described in a) above, the composition has a sufficient fungicidal effect. Re-isolation from the tissue under the treated area was negative, i.e. no infection could be detected eight months after treatment, as evidenced by the therapeutic effect. The composition produced an excellent surface because the surface formed by the ee did not change 6 months after treatment, did not create any cracks. By the pressure of the cave, the layer tore, but the cave was not suppressed.

(c) Santar SM

No formation of resistant surface was observed. As a result of drying the cleaned area (xylenes), deep low openings were created which provided the possibility of penetrating the fungi. In the eighth month after treatment, Cytospora would recover in vital form *

d) Stepers' wax

Application was complicated and the lid often separated from the treated surface. It did not observe and suppress the fungus, and in addition, directly below the layer formed with the highest quality wax, ee found Cytoepora cincta myeelium.

Example IV

In open-field tests, smaller apricot branches infected 100 cytoepora cincta spores. Two weeks after injection, an aqueous solution of the composition of the invention was applied to 30 spots by spraying them two or three times to form a uniform layer. One week after treatment, an attempt was made to re-isolate the pathogenic fungus. The results are shown below:

re-isolation of sponge treated with 100% control

Re-isolation was performed by ee every 10 samples.

Example V

In open-field tests, in vivo penetration of the compositions of this invention was tested. The tests were carried out on separate branches of four- or five-year-old apricots. The following materials were applied to the freshly cut surface:

(a) the active material prepared from Benomyl, methyl methacrylate and hydroquinone according to Example 1;

(b) the final product of Example 1; and

(c) Santar SM.

CS 274 279 B2

After 24 hours after treatment, the surface was removed to a depth of 5 mm and another 5 mm thick slice was cut from the branch. It was found (see Table III) that it

- there was no inhibition in the case of Santar SM (inhibition zone),

the resin product (b) had an inhibition zone to a depth of 15 mm.

- the material (a) had an inhibition zone to a depth of 30 mm. Using the method described above, it was shown that those parts. fungicidal material penetrated into the wood- Table III penetration, mm Resin product 5 10 15 20 May 25 30 (prepared product from example 1) Effective material + + + - - aa (example 1) + + ♦ + + + Santar SM aa and · αααβ ae - -

The method of the invention is illustrated by the following examples.

Example 1

In a reactor equipped with a stirrer, 55 kg of methyl methacrylate and 20 kg of hydroquinone were stirred and 25 kg of Benomyl were added. The mixture was heated to 110 ° C and stirred for 1 hour. The biphasic reaction mixture was cooled to give 100 kg of product. The active material was used without additives as shown in Tables I and III.

The ee resin was produced as follows:

100 kg of sunflower oil fatty acids, 40 kg of pentaerythlt, 55 kg of phthalic anhydrides and 8 kg of xylene were mixed and refluxed at 220 ° C for 4 days (acidity max. 25 mg KOH / g). The resulting water was continuously removed by azeotropic distillation. Then, the mixture was cooled to 150 ° C and 180 parts by weight were added. white spirit to form a solution. The viscosity of the product at 20 ° C (Beaker No. 4) was 180 to 200 a. It obtained aa 383 kg of a solution that did not contain petrol.

The following ingredients have been added to the solution above and e:

100 kg of aluminum pigment (so-called ailver pigment).

kg of crushed silica (Asroail - 380), kg of cobalt naphthenic acid salt,

200 kg of silicone shellac and 70 kg of titanium dioxide.

The addition was performed with vigorous stirring.

The above mixture (total 421 kg) was mixed with:

320 kg of the above active material and 310 kg of the resin solution described above.

051 kg of the liquid product thus obtained could be used directly for the treatment of trees either by brushing or by spraying.

Example 2

The procedure of Example 1 was repeated, except that the following materials were used to prepare the active material a and:

Benomyl methyl methacrylate monomer

130 kg 150 kg

CS 274 279 B2 hydroquinone 40 kg.

To the product thus obtained, ee added the additives of Example 1. The product was suitable for the treatment of wounds.

Example 3

He repeated the aa procedure of Example 1 using the following materials:

(% by weight)

Triadimaphon 6 methyl methacrylate monomer 20 hydroquinone 4 resin solution (and white spirit) 28 aluminum pigment 10

Aaroeil-380 5 cobalt naphthenate 0,1 silcon shack 19,86 titanium dioxide 7.

The product was suitable for treating injuries of atoms against infections caused by fungi (e.g. powdery mildew). The effect was therapeutic and preventive.

Example 4

The reactor was equipped with a stirrer and 3 parts by weight were threshed. methyl methacrylate and 2 parts by wt. of hydroquinone and, after mixing, 3 parts by wt. Benomyl. Stirring was performed with nitrogen gas. A double-walled probe of 340 to 390 nm quartz UV flask was placed around the reactor. The flask was turned on and the solution aa stirred with nitrogen gas for 30 minutes. The resin and additives of Example 1 were added to the biphasic product aa.

The use of the product was the same as that of the composition of Example 1.

Example 5

1 part of Benomyl, 2 parts of methylmeth cover and 1 part of hydroquinone were charged to a reactor equipped with a reflux condenser. The mixture was stirred vigorously with nitrogen gas. The reactor was equipped with a quartz probe operating a 8,340 to 390 µm quartz flask. The radiation raised the temperature to 80 ° C. The refluxing of the mixture took 10 minutes, then ea and the mixture was cooled and the resin of Example 1 was added.

The product could be used to treat tree wounds and healing and preventive effects.

Example 6 základní as a base aa used 1- [2- (2,4-dlchlorophanyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-thiazole. 6 kg of this material, 8 kg of methyl methacrylate and 6 kg of hydroquinone were mixed in the reactor and heated to 110 ° C with stirring.

In a separate reactor, 40 kg of polyiacyanate propolymar (Oaemodur E-21) were dissolved in 11 kg of butyl acetate and mixed and 10 kg of aluminum pigment, 6 kg of titanium dioxide and 3 kg of finely divided silica (Aaroeil-380) under anhydrous conditions and under nitrogen. .

The roe ee was added to the active material described above and stirred until the ee received homogeneous roe (aai 30 minutes).

The thus-coated solution was filled from carbon dioxide pressure.

The mixture was suitable for preventive and curative action against powdery mildew, Urcinula necator and Guignardia bidwalli and produced a permanent and strong film. The protective layer remained

CS 274 279 B2 on a tree for more than one year without inhibiting its growth ·

Example 7

5 parts of methyl methacrylate, 0.5 parts of hydroquinone and 2 parts of Benomyl were mixed. The mixture was stirred with hydrogen gas, then cooled and exposed to 4 MHz laser beams for 30 minutes. Then, the reaction was interrupted, allowed to cool, and added to the product aa by the auxiliary flights of Example 1.

The thus obtained composition aa was applied to the wound surface.

Tissue sample testing did not show fungal growth.

Example 8

In a reactor equipped with a stirrer, 20 parts of methyl methacrylate and 2 parts of hydroquinone were mixed and 3 parts of N- (4-chlorophenoxy) -1,1-dlmethyl-1H-1,2,4-triazine were added as the basic active ingredient. of 1-ethanol. The mixture was stirred at 110 ° C for 1 hour and cooled and mixed with the resin and excipients of Example 6.

The product could be used as a spray or applied by a brush on the cleaned wounds of a tree. On the wounds excellent durability of the formulation was achieved.

Example 9 kg of Benomyl, 65 kg of butyl methacrylate monomer and 20 kg of hydroquinone and heated to 120 ° C for 1 hour. The mixture was cooled to 30 ° C and 26 parts of a solution containing 40% alkyd resin and 60% gasoline mixed and 0.5 kg of finely dispersed silica (Asrosil-380), 0.1 kg of cobalt naphthenic acid salt were added. 20 kg of methylated silicone shake weight and 7.0 kg of titanium dioxide were homogenized.

Example 10

6 kg of 1- [2- (2,4-dichlorophenyl) -4-propyl-4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,22 were stirred at 110 ° C for 50 minutes. Of 4-triazine, 8 kg of methyl methacrylate monomer and 6 kg of hydroquinone and cooled to room temperature.

10 kg of beeswax, 10 kg of paraffin, 10 kg of aluminum pigment (paraffin-coated) and 0.5 kg of finely divided silica (Asrosil-380) were dissolved in a separate vessel with gentle boiling and stirring, and added to the active ingredient. prepared as described above, homogenized and cooled to a paste-like product.

The product could be used as flesh wax when aa grafted fruit trees (apple, apricot, sour cherry) and inoculated grapevine and rose protected the grafting or inoculation site with grafting material and eliminated infection of Entypa armaciacaa and Cytospora cincta. No cancers were observed at the grafting site for one year.

Example 11

Oako base active material used a mixture of 3 parts of Benomyl and 3 parts of β- (4-chlorophenoxy) -or- (1,1-dimethylethyl) -1H-1,2,4-triazine-1-stanol and this material was introduced into by contact with methyl methacrylate and hydroquinonam as in Example 1 and then aa mixed with alkyd resin and additives.

The so obtained product was an excellent antlfungal wound treatment material which could and could be used against Eutypa armeniacae, Cytospora cincta and Stereum purpureum with good preventive and curative effect, for example on apricots.

Example 12 kg of 2,3-dicarbo-1,4-dlthicanthraquinone, 11 kg of methyl methacrylate monomer and

CS 274 279 B2 kg of hydroquinone was heated to 110 ° C for 75 minutes. The product aa was treated and the resin 8 with excipients as in Example 1.

The product of the mass has preventive and curative effects against diseases caused by fungi in peach trees.

Example 13 kg of Triphorin, 8 kg of methyl methacrylate and 6 kg of hydroquinone were heated to 110 ° C for one hour. The mixture was cooled and a gasoline solution of polyurethane resin was added to a. After the addition of adjuvants, the product was used for the treatment of wounds against infections caused by fungi on peaches 8 by a therapeutic and preventive effect.

Example 14 kg of methyl methacrylate monomer, 1 kg of hydroquinone, 5 kg of copper amine (made from 1 mole of copper sulphate and 1 mole of triethylamine) and 1 kg of surface treatment sulfur and stirred and heated to 105 ° C for 1 hour, cooled and added 28 kg solution prepared from 60 parts gasoline and 40 parts alkyd resin. After addition of adjuvants As in Example 1, the product could be used on trees as a wound treatment material.

Example 15 kg of Tpeln methyl, 3 kg of methyl methacrylate, 1 kg of 1,2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl-1H-1,2,4-trlazine and 2 kg of hydroquinone was heated to 110 ° C for one hour, and after cooling, 7 kg of a resin solution prepared from 65 parts of gasoline and 35 parts of alkyd resin were added. To this, adjuvants as in Example 1 were added and mixed ae until aa reached a homogeneous emulsion. The product was filled into aerosol containers. 50 g of Freon 11 and 50 g of Freon 12a were added to 100 g of the mixture described above under pressure. The containers were sealed and fitted with a spray valve. The composition was sprayed onto a clean wound surface. An isolated sample taken after 8 months showed no fungal infection after a two to three incubation period.

Claims (1)

A fungicidal composition for combating and / or preventing diseases caused by fungi in the bark and woody tissue of a tree based vegetation based on a resin containing one or more fungicidally active compounds selected from the group consisting of benzimidazole, triazine, plperazine, cyanoacetic acid, MS9 and / or fungicides. sulfur, and their amsai, comprising an alkyl methacrylate and 1 to 4 carbon atoms in the alkyl moiety, hydroquinone, wherein the weight ratio of the fungicidal active ingredient to the methacrylate to the hydroquinone is from 3 to 12: 9 to 25 to 1 to 9, and longer it contains, based on the amount of said components, 10 to 300% by weight of a resin selected from the group consisting of alkyd, apoxy, atyran, silicone and / or polyurethane resins and tar, and / or vacuum.