Technical field

The present invention relates to novel compositions for the treatment and prevention of plant diseases caused by plant-parasitic fungi living on the bark and woody tissues of arborescent vegetation.

Another object of the invention is the preparation and use of the novel plant protecting compositions .

Background art

On arborescent vegetation, mainly Qrnamental anl fruit trees of the moderate zone certain fungal infections destructing the bark , phloem and cambiums of trees are -widely spread ; the se pathogen often penetrate into the xyleme . The se infections may cause the partial or total destruction. These infections can cause great economical damages ; No sufficient chemical protection has been applied so far . The available treatment materials provide a limited or preventive protection only. The treatment provides only a provisional control of the pathogens and the renewal of injury may be expected .

Likely, parasitic fungi also re sult in substantial destruction in cordon cultivation of vineyards . Different effects may cause injurie s on the bark , like frost damages , bark etoliations caused by the sun, fractions caused by snow , ice , cultivating tools , vibrators , etc ., open wounds , bites of animals , damages by insects living in the plant tissues or open wounds caused by pruning. Malign surface injuries caused by fungi should also be considered . These "open doors" provide an easy way for insects and parasitic fungi to penetrate into the plant and thus , causing serious infections .

In the intensive gr owth period , the natural immuno system of

plants is rapidly activated by the biochemical and hiτological changes on the wound area and the infection is suppressed. However, in the resting period no or very small defenc e reaction takes place . A part of fungi appearing on the wound surface and the spores can cause infection even at 0 C .

It is also known that a large number of fungicides of different types are available . These , however, exert their effect only when taken up through the leaves or roots or provide a surface protection only. For example , the systemic fungicide , Benomyl had been test¬ ed against different pathogenic fungi, mainly against Cytospora leucost causing the Cytospora carcinoma of peach . A control was possible only if performing the treatment before infection: the infection already developed could not be reversed ; the plant could not be cured. The reason of the ^" aforesaid effect is that only a surface protection could be provided and the composition did not penetrate through the bark and phloem Plant Disease Reporter 60 /1 976/ 4.77-4-797. Radioactive studies on American aim /Ulmus americana/ showed that both the penet ion through the sprouts and the translocation is of low level /Chemical Central Res . Ins . Ottawa , Canada , Information Report CC- -4-7 , 1972

The present invention aims to provide a composition which is applicable to control parasitic fungi living in the bark and woody tissues of arbore scent vegetation and meets the f ollowing requirements :

- no phytotoxicity, - provides a broad and prolonged fungicidal effect,

- forms a durable protecting layer which does not get split and washed down by the sun and rain, resp. ,

- besides the preventive effect possesses a curative effect as well , i. e . is able to penetrate into the woody tissue through the bark and phloem.

Disclosure of the Invention

It has been found that a composition meeting the above requirements may be prepared by interacting one or more fungistatic chemicals /basic active material/ and alkyl methacrylate in the presence-of cross-linking inhibiting compound /s / by energy transmissio and mixing the product thus obtained in the presence or absence of organic solvent with a re sin and /or wax.

As fungicidal active compounds both the systemic and non- systemic fungicides may be used: the penetration is provided by the formation of the material obtained b y interaction with the alkyl methacrylate and inhibitor .

Examples of fungicides are the benzimidazol and triazine derivatives , copper- and /or sulfur- containing fungicides , cyanoacetic acid derivatives , the mixtures of the above fungicides , etc. Preferred fungicides are the following commercially available compounds:

Methoxycarbamoyl benzimidazole , Benomyl , Captafol , Zineb , Thio- phanate -methyl , Procymidon, 2-n-octyl-n-isothiazolin-3-on, Cursate , copper oxychloride , Fenarimol , Captan, Metiiathion , 8-oxyquinoline sulfate , Triphorin, Iprodion, Vinchlozolin and the mixture /s / thereof. Resins are e . g. the synthetic resins such; -as the alkyd , epoxy, styrene , silicon and /or polyurethane resins and tar . Examples of wax are: paraffin, natural waxes /Canada balsam , beeswax , Carna ba vax/. Natural resins,e . g. shellac can also be used .

According to the invention the preferred inhibitors may be the hydroquinσn, hydroquinon- derivatives , ascorbic acid , phenol an i phenol derivatives . These compounds , besides inhibiting the non-desire polymerization of the alkyl methacrylate , also possess a certain bacterio static 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 preferably 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 under 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 methacrylat , 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 4-88 nm line at a performance of 1 W the reaction take s place in 2 to 3 hours . By using an apparatus of 4. W performance /6 laser lines enter the reaction area together/ the reaction time decreases to 30 to 4-0 minutes.

This reaction mode eliminates the need of heat energy and the reaction can safely be controlled.

Ac cording 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 material thus obtained is mixed with resins of different type to obtain the 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 the other materials , if desired, under 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 inhibitor, alkyl methacrylate and basic active material before cooling.

Suitable solvents for this purpose , depending on the type of the resin are : gasoline , xylene , toluene , petroleum, paraffin oils , buthyl acetate , higher alcohols , etc .

The concentration of the said resin solutions is preferably 4-0 to 70 % by weight. The pre ferred wound treatment resin contains

50 to 80 % by weight of resin .

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 explosed to UV light.

In case of using the composition in the form of paste or viscous solution , preferably a pigment or pigment -containing agent is added to the system, especially for protecting against Uv -light. Such additives are e . g. the metal pigments , like aluminium, bronze , copper alloys , manganese , etc . Other suitable pigments are the oxides , such as titanium dioxide , aluminium oxide , barium oxide or finely divided silica, as well as the micae such as aluminium phosphatide , calcium phosphatide , etc .

The invention also relates to any composition for the treatmen of bark and hadrome which contains , as active ingredient, a mixture of alkyl methacrylate , basic active ingredient and cross -linking inhibiti agent /inhibitor/ having been prepared by energy transmission and at least one resin or wax.

The wood treatment compositions according to the invention may also contain further well-known auxiliaries .

The composition is applied on the surface to be treated in a layer of 10 to 2 mm thickness . The composition according to the invention provides protect¬ ion against secondary fungal infections for 2 to 3 years , thus , prevent¬ ing e . g . the secondary settlement of wood -rotting fungi. It provides not only protection but also curative effect against many fungus strains attacking the phloem from the inside . The biological activity of the composition according to the invention was tested against various plant diseases caused by fungi, among others :

- branch carcinoma caused by Cytospora cincta and tree destruction on peach , apricot, cherry and sour -cherry , - carcinoma caused by Phacidiella discolor on apple and pear,

- "black carcinoma" caused by Sphaeropsis malorum on apple and pear,

- carcinoma caused by Nectrina galligena on apple and pear. As the infectious fungi are wound-parasitic, the treatment of wounds and the skilled use of the materials for treatment plays an important role in the protection.

In vivo laboratory tests of the compositions were carried out on potato -dextrose medium in Petri plates . The medium was inoculated on 3 spots and incubated for 3 to 5 days , depending on the growth velocity. After incubation, a hole was made at the centre of each plate and 0, 1 ml of test material was dropped therein. The plates were subsequently incubated until the untreated control plates become complet overgrown. Evaluation of the fungicidal effect was accomplished by measuring the inhibition zones . Table I shows the effect of the product

pbta ined according to Example 1 /MBH/ on different fungi. The composition labelled as MBH showed a total inhibition against each fungus.

As comparison, the biological effects of the single com- ponents of the composition Benomyl -methyl methacrylate -hydroquinone

-alkyd resin have also be determined . It has been found that none of the Benomyl -hydroquinone system, the methyl methacrylate -hydro¬ quinone system and the Benomyl -methyl methacrylate system showed an effect comparable with that of the compositions according to the invention.

When omitting the hydroquinone , the Benomyl should have been kept suspended in the fluid monomer by continuous stirring in order to avoid sedimentation and discoloration. The thermal treatment of the Benomyl -hydroquinone system could only be performed in the. presence of a solvent. For example , thermal treatment of Benomyl and hydroquinone in the presence of toluene at 110 C for 48 hours yielded a mixture , the biological activity of which did not exceed that of the Benomyl, i. e . only a surface activity was obtained .

B st Mode of Carrying out the Invention

Biological examples

The biological effect of the compositions according to the invention was tested against the following fungi:

_Fungus^ _ from

Cytospora cincta peach Sphaeropsis malorum apple

Phomops.s mali apple

Phacidiella discolor - pear

/cont. /

Chondrostereum purpureum apple Eutypa armeniacae apricot Pezicula malicorticis apple .

For comparison, the biological effect of the commercially available Santar SM was also tested .

Table I .

Example I

Fungus Untreate d Product of Santar SM Produc control Example 1 Exampl

Cytospora cincta 0 TI 20 % ^' - TI

Phomopsis mali 0 TI 5 % T I

Sphaeropsis malorum 0 T I 20 % TI

Stereum purpureum 0 T I 20 % 0

Phacidiella discolor 0 TI TI TI

TI = total inhibition;

% some inhibition occured around the composition; this is expressed in the % of area . Over the inhibition zone the vitality of fungus rem unchanged ;

0 = no inhibition , the plate is overgrown.

Table II.

Example II

Fungus Untreated Product of Exampl control

Cryptosporiopsis corticola 0 TI

Crypto sporiopsis malicorticis 0 TI

Diplodia sp. 0 . SI

Eutypa armeniacae 0 TI

Coryneum micro stictum 0 TI Libertella blepharis 0 TI

Stereum purpureum 0 SI

SI - strong inhibition.

Example III

Open-air tests were carried out to determine the biological effect of the compositions according to the invention.

Cancerous wounds of peach trees infected with Cytospora cincta were cleaned up as deep as the healthy tissues and the compositi were applied as viscous fluid by brush on the surface . As comparative material, commercially available Santar SM was used. The following results were obtained: a/ Product of Example 1

In the eighth month after treatment tissue fragments obtained from the infected and treated tissues were passed on sterile PDA medi

It was found that no mycelium remained in the xyleme which shows the curative effect. No inhibition of callus formation was detected. The product possessed an excellent fungicidal effect. b / Product of Example 6 According to the test under a/ as above , the composition showed sufficient fungicidal activity. The re -isolations from the tissues under the treated area were negative , i. e . no infection could be detected 8 months after treatment: a proof of the curative effect. The composition forms an excellent surface : the surface formed by the composition has not changed 6 months after treatment; no slits were formed . By pressure of the callus formed the layer broke : the growth of callus was not inhibited . c/ Santar SM

The formation of durable surface was not obser-ved. Due to drying of the cleaned area /xylem/ deep slits were formed providing a possibility for penetration of fungi. Ln the eighth month after treatment the Cytospora could be re -isolated in vital form. d/ Grofting wax

The application was complicated and the wax frequently separate from the treated area. No inhibition of fungi was observed ; moreover, directly under the layer formed by the wax great quantities of Cytospora cincta mycelium were deposited.

Example TV

In open-air tests , branches of peach jvere infected with Cytospora cinc ta on 100 spots . Two weeks after infection the aqueous solutions of the composition according to the invention were applied on 30 of the spots by spraying the solution twice or three times so that

a uniform layer was formed. One week after treatment attempt was made to re-isolate the pathogenic fungus . The results are shown herebelow:

Re -isolated fungi: treated 0 control 100 %.

The re -isolation was carried out with each 10 samples .

Example V

In open-air tests the penetration of the compositions according to the invention were examined in vivo. The test was carried out on removed branche s of 4 to 5 years old peach trees . On the freshly sawn surface the following materials were applied: a/ the active material prepared from Benomyl , methyl methacrylate and hydroquinone according to Example 1 , b / the end product of Example 1 , c/ Santar SM .

After 24 hours the treated surface was removed in a depth of 5 mm and additional slices of 5 mm were cut from the branch. The disks , after surface flaming , were placed on PDA medium inαculat ed with the conidia of Penicillium cyclopi.tm and incubated at 26 C for 48 hours . It was established /see Table III/ that

- in case of Santar SM no inhibition /inhibition zone / was obtained ,

- the resin product /b / showed an inhibition zone to a deepness of 15 mm,

- the material /a/ showed an inhibition zone to a deepness of 30 mm.

By using the above method it was demonstrated that the fungic material had penetrated into the woody parts .

Table III

Penetration mm 5 10 15 20 25 30

Resin product

/formulated product of Example

1 / + + + - . _

Active material

/Example 1/ + + + + + +

Santar SM - - -

The process according to the invention is illustrated by the following examples : ^'

Example 1

In a reactor provided with stirrer 55 kg of methyl me hacrylate and 20 kg of hydroquinone are mixed and 25 kg of Benomyl was added. The mixture was heated to 110 C and stirred for one hour . The two- phase reaction mixture was cooled, thus obtaining 100 kg of product. This active material was used without additives as shown on Tables I and IH.

The resin was prepared as follows: 100 kg of sunflower fatty acid, 40 kg of pentaerythrite , 55 kg of phtalic anhydride and 8 kg of xylene were mixed and refluxed at 220 °C for 4 hours /acidity max. 25 mg KOH /g/ . The water produced was continuously removed by azeotropic distillation. Then the mixture was cooled to 150 C and 180 parts by weight of white spirit was added to form a solution. The viscosity of product at 20 °C /beaker No . 4/ wa

180 to 200 sec. 383 kg of gasoline -free solution was obtained.

To the above solution the following additives were added: 100 kg of aluminium pigment /so-called " silver pigment" /, 50 kg of Aerosil-380 /finely divided silica/, 1 kg of cobalt naphtenate ,

200 kg of silicon lat , 70 kg of titanium dioxide .

The addition was performed during vigorous stirring.

The above mixture /a total of 421 kg/ was mixed with - 320 kg of the aforesaid active material and

- 310 kg of the above re sin solution.

The 1051 kg of fluid product thus obtained can directly used for the treatment of tree s either by brushing or by spraying.

Example 2 The proce ss of Example 1 was repeated with the difference that for preparing the active material the following materials were use

Benomyl 130 kg methyl methacrylate monomer 150 kg hydroquinon 40 kg . To the product thus obtained the additives according to Examp were added. The product was suitable for wound treatment.

Example 3

Following the process of Example 1 the following materials were used:

11% by weight/

T riadimephon 6 methyl methacrylate monomer 20 hydroquinon 4 resin solution /with white spirit/ 28 aluminium pigment 10

Aerosil-380 5 cobalt naphtenate 0, 1 silicon lac 19, 86 titanium dioxide 7 .

The product is suitable for wound -treatment of trees : against fungal /e. g. powdery mildew/ infections . The effect is curative and pre entive .

Example 4 hi a reactor provided with a starrer 3 parts by weight of methyl methacrylate and 2 parts of hydroquinon were placed and after stirring 3 parts of Benomyl was added. The stirring was accomplished with nitrogen gas . A double walled quartz sound provided with a 3400 to 3900 A quartz UV bulb was placed into the reactor . The bulb was switched on and the solution was stirred with nitrogen gas for 1 /2 hour.

To the two-phase product the resin and additives of Example 1 were added .

The use of the product is similar to that of the composition of Example 1. Example 5

In a reactor provided with a reflux cooler 1 part of Benomyl, 2 parts of methyl methacrylate and 1 part of hydroquinon were added . The mixture was vigorously stirred with nitrogen gas . The reactor was provided with a quartz sound functioning with a 3400 to 3900. _i quartz

bulb. The irradiation raised the temperature to 80 °C. The mixture was refluxed for 10 minutes then stopped, the mixture was cooled and the resin of Example 1 was added.

The product can be used for treating the wounds of trees wit curative and preventive effect.

Example 6

As basic material l-/ ^r __-/2,4-dichloro-phenyl/-4-propyl-l,3- -dioxolan-2-il-methy_7-lH-l,2 ,4-triazine was used. 6 kg of the above material, 8 kg of methyl methacrylate and 6 kg of hydroquinon were mix and heated in a reactor at 110 °C for one hour while stirring.

In a separate reactor 40 kg of polyisocyanate prepolymer /Desmodur E -21/ was dissolved in 11 kg of buthyl acetate and mixed with 10 kg of aluminium pigment, 6 kg & f titanium dioxide and 3 kg of finely dispersed silica /Aerosil-38θ/ under anhydrous conditions and in nitrogen atmosphere .

The mixture was added to the above active material and stirr until a homogenous mixture was obtained /about 30 minutes/.

The solution thus obtained was filled under carbon dioxide pre

The mixture is suitable for preventive and curative treatment against powdery mildew, Urcinula necator and Guignardia bidwelli and forms durable and strong film. The protective layer remained on the tr for more than one year, without inhibiting the growth thereof.

Example 7

5 parts of methyl methacrylate , 0,5 parts of hydroquinon and 2 parts of Benomyl were mixed. The mixture was stirred with hydrogen gas, then cooled and exposed to 4 MHz laser ray for 30 minutes . The reaction was interrupted, the mixture cooled and the auxiliaries accord to Example 1 were added to the product.

The composition thus obtained was applied on the surface of wounds: the medium assay of tissue samples did not show fungal growth.

Example 8 In a reactor provided with stirrer 20 parts of methyl methacryla and 2 parts of hydroquinon were mixed and as basic active ingredient 3 parts of beta-/4-chlorophenoxy/-alfa-l, l-dimethyl-lH-l ,2,4-triazin- -1-ethanol was added. The mixture was stirred at 110 C for one hour, cooled and mixed with the resin and auxiliaries of Example 6. The product can be applied as spray or by brush on cleaned tree wounds . An excellent durable wound -treatment composition was obtained .

Example 9

15 kg of Benomyl, 65 kg of buthyl methacrylate monomer and 20 kg of hydroquinon were heated at 120 C for one hour. The mixture was cooled to 30 C and 26 parts of solution consisting of 40 % of alkyd resin and 60 % gasoline mixed with 0,5 kg of Aerosil-380, 0, 1 kg of cobalt naphtenate , 20 kg of methyl base silicon lac and 7 , 0 kg of titanium dioxide were added and homogenized.

Example 10

6 kg of l- 2- /2 ,4-dichlorophenyl/-4-propyl-l,3-dioxolan- -2-yl-methy^ ^' -lH-l,2 ,4-triazine , 8 kg of methyl methycrylate monomer and 6 kg of hydroquinone were stirred at 110 °C for 50 minutes and cooled to room temperature . In a separate vessel 10 kg of beeswax, 10 kg of paraffin, 10 kg of aluminium pigment /covered by paraffin/ and 0,5 kg of finely divided silica /Aerosil-320/ were dissolved under slight warming and stirring. The mixture thus obtained was added to the above active material, homogenized and cooled, thus obtaining a paste -like product.

The product can be used as grofting wax when grofting fruit trees /apple , apricot, cherry/ and at budding of vine and rose for prote ing the place of grofting and budding. Eliminates the Entypa armeciacae and Cytospora cincta infections carried by the grofting material. No carcinoma could be observed on the groftlings in one year.

Example 11

As basic active material, the mixture of 3 parts of Benomyl and 3 parts of beta- /4-chlorophenoxy/-alfa- /l , l-dimethyl-ethyl/- 1H- -1,2 ,4-triazine-l-ethanol was used and brought into contact with the methyl meth&crylate and hydroquinon as in Example 1 followed by mixing with alkyd resin and additives .

The product thus obtained has excellent antifungal wound treat¬ ing material which can be used against Eutypa armeniacae , Cytospora cincta and Stereum purpureum with good preventive and curative effect, e . g. on apricot trees .

Example 12

3 kg of 2 ,3-dicarbo-l ,4-dithio-anthrachihon, 11 kg of methyi, methacrylate monomer and 6 kg of hydroquinon were heated at 110 C for 1 1/4 hours . The product was formulated with resin and auxiliaries as in Example 1.

The product has preventive and curative effects against fungal infections on peach trees.

Example 13

6 kg of Triphor n, 8 kg of methyl methacrylate and 6 kg of hydroquinon were heated at 110 C for one hour. The mixture was coole and a gasoline solution of polyurethane resin was added thereto. After the addition of auxiliaries the product was used for wound treatment against fungal infections on peach with curative and preventive effect.

Example 14

20 kg of methyl methacrylate monomer, 1 kg of hydroquinon, 5. kg of "copper amine" /prepared from 1 mole of copper sulfate and 1 mole of triethyl amine / and 1 kg of surface treated sulfur were mixe and heated at 105 °C for one hour , cooled and 28 kg of a solution prepared from 60 parts of gasoline and 40 parts of alkyd resin was added thereto. After the addition of auxiliaries as in Example 1, the product can be used on trees as wound treating material.

Example 15 1 kg of Top sin methyl, 3 kg of methyl methacrylate , 1 kg of

1 , 2-/2, 4-dichlor ophenyl / -4-proρyl -1 ,3 -dioxolan -2 -yl -me thyl- 1H - -1,2 ,4-triazin and 2 kg of hydroquinon were heated at 110 °C for 1 • hour. After cooling, 7 kg of resin solution prepared from 65 parts of gasoline and 35 parts of alkyd resin was added. The auxiliaries accor to Example 1 were added and stirred until homogeneous mixture was obtained. The product was filled in aerosol containers and 50 g of product Freon 11 and 50 g of Freon 12 were added to 100 g of the abov mixture under pressure . The container was sealed and provided with spraying valve. The composition was sprayed on cleaned surface of wounds . The isolated sample taken after 8 months did not show fungal infection in 2 to 3 days ' incubation period.