Composition for seed pickling and method for controlling of plant diseases

The present invention relates to a new composition for seed treatment, containing as active substances tebuconazole and thiabendazol, more specifically to a new preparative form of water suspension concentrate, comprising, in addition to the active ingredients necessary to obtain this formulation components.

The tebuconazole - common name of the active substance systemic broad-spectrum fungicide (formula I)-(RS)-1-(4-chlorophenyl)-3-(1,2,4-triazole-1-yl-methyl)-4,4-dimethyl-pentane-3-ol. Crickets seeds on the basis of tebuconazole known under the trademark Raxil® (trademark of Bayer.) (see EP 0040345, US Pat. No. 4723934, DE OS3333411, Pflanzenschutz Nachr Bayer, 40.2.81-129).

Thiabendazol - common name of active ingredient of fungicide contact action (formula II) - 2-(4^'-thiazolyl)benzimidazole, first obtained from Merck & Co (United Kingdom Patents No. 1071421, France No. 2014326, USA No. 3017415 from 16.01.1962 year).

It is known that as tebuconazole and thiabendazol widely used in combination with other fungicides or substances with a different activity, including for presowing treatment of seeds. This allows to expand the range of drugs, and also to some extent to counteract the already acquired resistance against an individual acting the substances (See, for example, EP 0275013, EP 0316970, EP 0393746, EP 0423566, EP 0487451, EP 0897665, EP 0271579, US Pat. No. 4906648).

As for known mixtures of tebuconazole and thiabendazole, microbicide combination of tebuconazole and thiabendazole, which is added to the original components in the polymerization process to protect receiving technical materials described in EP 0522393. In EP 0539332 mentioned about the possibility of using a mixture of thiabendazole and tebuconazole to protect Luke from the disease caused by the pathogen Sclerotium cepivorum. Any information about formulation and the effectiveness of their action against plant pathogens in these sources are not available.

The closest the present invention to the technical essence is the composition for seed treatment in the form of a water-suspension concentrate containing as active substances (E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazole-1-yl)1-penten-3-ol (diniconazole) and 2-(4 thiazolyl)benzimidazole (thiabendazole) in the ratio of 1-2:2-1 in combination with other components that provide the necessary consumer properties of the drug as a fungicide seed. This composition (prototype), described in the patent of the Russian Federation No. 2206204, is a highly effective drug that protects crops against a wide spectrum of diseases, however, has certain disadvantages.

The PE is o, the presence in the commercial diniconazole about 20% (+)-optical isomer with herbicide and retardante properties, has a definite negative effect on crop quality, growth and development of plants, especially in the early stages. In addition, the necessity of use of the composition required for their additional technological operations optically active (-)enantiomer leads to higher prices for the drug.

Secondly, the drug was not sufficiently stable under conditions of prolonged storage at low and high temperatures.

Finally, indicators of uderzhivaemoi drug on seeds during storage was not high enough.

These disadvantages lacks new and improved composition for seed treatment in the form of a water-suspension concentrate, which is an object of the present invention.

In the composition for seed treatment according to the present invention as active ingredients used tebuconazole and thiabendazol in a ratio of 20:1-1:20 with the content of active substances from 2.0 to 40.0 wt.%.

Unlike the prototype instead of diniconazole in the form of the (-)enantiomer composition contains its close structural analogue - tebuconazole. Unlike diniconazole the tebuconazole recommended for use in the form of a rat is standard mixture (50:50) (-)-S and (+)-R optical isomers. As shown by the experiments, crop quality processed new fungicide seed has improved. It was possible to expand the range of ratios of active substances and their contents in the preparative form.

Stability of the drug in conditions of prolonged storage at high and low temperatures were achieved by the partial or complete replacement of propylene glycol in glycerin, which is injected in an amount of from 0.5 to 20.0 wt.%. In addition to lowering the freezing temperature of the glycerol in the new song plays the role of "gravity" component, which provides the alignment of the densities of all the contained components. In addition, glycerol is a homogenizing agent to enter into the composition of mineral or vegetable oil.

Add in the formulation of disinfectants mineral or vegetable oil in an amount up to 15 wt.% provides education on the treated seeds of a homogeneous film, which leads to uniform distribution of fungicides on the entire surface of the caryopsis.

It also turned out that along with the addition of the oil introduction in receipt of a small amount dibutil or dioctylphthalate (up to 5 wt.%), the so-called "samalia-EES", increases the fixation of fungicide on the seed surface and increases stability treated with the s seeds to mechanical abrasion. Often after repeated pouring or simply during storage of treated seeds with them showered dye and fungicide, which further reduces the resistance of crops to various diseases. Field tests have shown that after the introduction into the composition of the above components are formed is capable of withstanding prolonged mechanical abrasion without changing fungicidal activity.

As wetting, dispersing agents, thickeners and antispyware patentable composition, in addition to the components specified in the prototype, can also contain their counterparts on the chemical structure and nature of the actions that are interchangeable when used for its intended purpose.

As wetting, in addition to Rodosha 860/R was other suitable nonionic surfactants from the group polyethoxysiloxane and politprosveshenya fatty alcohols and alkyl phenols, such as Vitanol NP (trademark of AKZO-Nobel) (Akzo Nobel Surface Chemistry LLC Witconol NP-80/ Ethoxyleted Nonyl Phenol), Igepal VS (trade mark of the company Rhodia) (Surfactants and Specialites for Plant Protection, Rhodia) and well-known domestic emulsifiers OP-7 and OP-10 and Neonol (Surfactants. Handbook edited Art and Gamgebeli. Leningrad, "Chemistry", 1979; Surface-active substances and compositions. Handbook Ed. by M. letnev, Moscow, OOO firm Clavel, 2002).

As a dispersant, in addition to Saprovore fluorescence, can be used other anion active surfactants from the group of amine salts of di - or christiantamilringtonesj esters of phosphoric or sulfuric acids, such as Suprior 3D/33, Suprior 4D/ 384 and Suprior BCA/7, which are interchangeable for this formulation (Surfactants and Specialites for Plant Protection, Rhodia).

As thickeners, except Rhodopol 23, can be applied to other polysaccharides, including cellulose thickeners, such as Bermocoll® (trademark of Akzo-Nobel) of Akzo-Nobel (ethoxylated cellulose ethers) (Brief technical description Bermocoll®. Cellulosic thickeners. Akzo Nobel) and domestic carboxymethyl - or karboksimetilcelljulozy (Surfactants. Handbook edited Art and Gamgebeli. Leningrad, "Chemistry", 1979).

As a non besides Rodoreda was possible with the same result, to use domestic polydimethylsiloxane antifoam Penta 469.

It also turned out that the composition of a new composition allows to use not only water-soluble dyes such as Cationic red 2C, but water-insoluble, the so-called lucky, including Lacquer ruby SC and Varnish Rubin SC, representing the calcium salt of 2-hydroxy-4-[(4-methyl-2-Sul is o(phenyl)]-azo-2-naphthaleneboronic acid (GOST 7436-74).

When added to the composition of varnishes it remains homogeneous, and when applied fungicide on grain achieves a uniform dispersion staining protravlivanija material.

As a preservative in a new composition used in the same Kobata With® (trade mark of the company Rhodia) or its full equivalent of Globull (trade mark firm Rhome and Haas).

Thus, an object of the present invention is a new composition for seed treatment in the form of a water-suspension concentrate containing as active ingredients a mixture of tebuconazole (I) and thiabendazole (II) in an amount of 2.0 to 40.0 wt.%, with a ratio of I:II is from 1.0: of 20.0 to 20.0: 1.0 in.

As the wetting composition contains at least one nonionic surfactant selected from the group polyoxyethylene or politprosveshenya alcohols or polyoxyethylenated ALKYLPHENOLS, including Nadasurf 860/R, Vitanol NP 80, Igepal SU 10 and OP-7 or OP-10 or Neonol, in the amount of from 0.1 to 5.0 wt.%.

As the dispersant composition contains at least one anion surface-active substance selected from the group of ammonium salts of di - or christiantamilringtonesj esters of phosphoric or sulfuric acids, including Suprior FL, Suprior 3D/33, Suprior 4D/384, Suprior BCA/7 in the amount of from 1.0 to 15.0 wt.%

As thickeners composition may contain anion is the first heteropolysaccharide Rhodopol 23, or nonionic derivative of cellulose Bermocoll in the amount of from 0.1 to 10.0 wt.% or carboxymethyl - or carboximetilzellulozu (in terms of a 2% solution of thickening agent).

As a preservative in the composition used hexahydro-1,3,5-Tris(2-hydroxyethyl)Symm.-the triazine in number to 0.045 wt.% (Kobata With or Glocker).

As the non use polydimethylsiloxane (Rodosil 426 or Penta 469).

To obtain the signal of color in the composition of the injected dye or water-soluble (cationic red 2C), or water-insoluble (Lac Rubin SC or SC) in an amount of not more than 25 wt.%.

Unlike the prototype of a new composition as antifreeze and co-solvent comprises glycerin in an amount of from 0.5 to 20.0 wt.% or its mixture with propylene glycol, and the content of the latter does not exceed 10 wt.%, and the ratio of glycerol and propylene glycol is from 1:0.1 to 0.1:1.

Unlike the prototype of the new composition also contains mineral (transformer, vaseline, industrial) or vegetable oil (soybean, vegetable) in an amount of from 0.5 to 15.0 wt.%, and the so-called sizing, at least one of the esters of phthalic acid (dibutil, dipropyl or dioctylphthalate) in an amount of 0.01-5.0 wt.%.

The introduction of glycerin and oils in the composition, as shown by the experiments, increases its agregation the Yu stability and increases frost resistance. New drugs unlike the prototype can be stored without changing the properties at temperatures from minus 10°C to + 35°and exhibit high resistance to heat aging.

Add oil and oil ensures uniformity of staining and a high degree of uderzhivaemoi drugs on the seed surface, which leads ultimately to increase the effectiveness of their action against pathogens that cause plant diseases.

A mixture of tebuconazole and thiabendazole in different ratios, as shown by the experiments, but is not inferior to the prototype of both the level and spectrum of biological activity, although unlike the prototype of a mixture of active substances not find such a significant and explicit synergies in relation to the causative agents of plant diseases.

The field of biological testing patentable composition showed high biological efficacy against root rot of spring wheat and barley, and efficiency of patentable composition against rot Helminthosporium was much higher than the efficiency of the drug on the tebuconazole (drug Raxil) due to the presence of the second fungicide - thiabendazole. The drug also showed high efficacy against the most dangerous diseases of cereal crops is dusty and hard.

In General, we can say that the proposed composition of the drug on the basis of tebuconazole and thiabendazole showed high efficacy against pathogens placevine fungi (Rhizopus spp., Penicillium spp., Trichothecium spp.), fusariose-snow mold (Fusarium culmorum, F.oxysporum, F.graminearum, F.avenacium), fusariose-Helminthosporium rot, bacterial diseases (Pseudomonas spp., Xhanthomonas spp., Corynebacterium spp.), protection from diseases (Ustilago nuda, Ustilago laevis, Tilletia tritici, Sphacelotheca panici on miliaceae, Ustilago zeae, Sorosporium reilianum) cereal, maize and millet.

Experiments have also shown a beneficial effect of a new drug on the quantity and quality of wheat and barley.

Another object of the invention is a method of combating plant diseases by pre-sowing seed treatment an effective amount of the above composition.

This is followed by examples illustrating, but not limiting the invention.

Example 1. A composition for seed treatment.

The reactor is heated predetermined amount of propylene glycol, glycerol, wetting agent, dispersant and non and mix thoroughly. To the resulting mixture add tebuconazole, thiabendazole, oil, lubricant and water and mix thoroughly. The resulting mixture is ground in a bead mill, dyno-mill until the particle size of m is 5 μm. Milled suspension is served in the capacity to which is added the estimated amount of the previously prepared 2% solution of thickener containing the required amount of preservative and the estimated amount of dye. After adding all components, the mixture is again thoroughly mixed.

In table 1 presents some of the formulas derived drugs.

^andNadasurf 860/P

^bSuprior 4D/ 384

ⁱⁿRhodopol 23

^gKobata

^dCationic red 2C

^eVaseline oil

^WThe dioctylphthalate

^CRodosil 426

^andIgepal sun/10

^toSuprior FL

^lOil transformer

^mSuprior 3D/33

ⁿLacquer ruby SC

^aboutIndustry oil

^pBermocoll

^RDibutyl

^withPenta 469

^tVitanol NP 80

^ySuprior BCA/7

^fGlocker

^xLacquer ruby SC

^CDIPROPYLENE

^hOP-7

^WCarboxymethylcellulose

^shchKarboksimetilcelljuloza

^üSoybean oil

As examples of the obtained formulas can cause the following structures:

Composition 1.

Physico-chemical characteristics of the drug:

Part 2.

Physico-chemical characteristics of the drug:

Part 3.

Physico-chemical characteristics of pre is Arata:

Part 4.

Physico-chemical characteristics of the drug:

Part 5.

Physico-chemical characteristics of the drug:

Composition 5*

Physico-chemical characteristics of the drug:

Part 6.

Physico-chemical characteristics of the drug:

Example 2. Evaluation of the stability of drugs during storage.

To assess the possibility of storing drugs for 2 years at a temperature of from minus 10 to plus 35°conducted the following tests:

1. Test accelerated storage: drugs kept in a thermostat at plus 54°C for 2 weeks (method CIPAC MT 46);

2. Test for frost resistance: the drugs were kept in a thermostat at a temperature of minus 15°C for 10 days (GOST 9.707-81 and Surfactants and Specialties for Plant Protection, Rhodia);

3. Test heat ageing: the drugs were kept in a thermostat at a temperature of 45°60 days (GOST 9.707-81 and Surfactants and Specialites for Plant Protection, Rhodia);

The repetition of the tests is 3-fold.

The viscosity of drugs both before and after storage was determined on a Brookfield viscometer, stability was determined by the GOST 16484-79 and Method CIPAC MT161, the dispersion was determined by a laser particle analyzer Fritsch-Analysette 22. The results are presented in table 2.

As can be seen from table 2, the new composition is superior to the composition of the prototype in terms of frost resistance and resistance to thermal aging.

Example 3. Study of biological activity in in vitro experiments (pure cultures)

The experiments were carried out in respect of such pathogens of cereal crops as Fusarium frost, Botritis cinerea and Pseudomonas atrofociens.

In a Petri dish filled with planted them in colonies of fungi were placed etched preparations of the seeds were kept in the incubator for 3-5 days. After curing was measured zone decontamination of colonies of fungi, comparing the growth of colonies in control and on the environment entered into them protravlennye seeds before and after mechanical abrasion.

For the mechanical abrasion of the treated seeds used mechanical vibrator, which established the sieve containing the seeds treated, and carried out the course vibrating processing for 15 minutes at a frequency of 35-50 vibrations per second.

As can be seen from table 3, patent-pending blend in the form of the drug in the form of a water-suspension concetrate had a higher fungicidal activity than the reference drug on the basis of one of tebuconazole (raxil, VSC). Analysis of resistance to shattering of seeds after mechanical in the action, certainly shows the improvement of these characteristics in patentable compositions compared with standard - Maxilom and drug prototype based on a mixture of diniconazole and thiabendazole.

Example 4. The effect of disinfectants on crop quality, growth and development of barley.

The experiments were carried out in laboratory conditions in accordance with the guidance for conducting greenhouse and field trials, seed disinfectants, fungicides and bactericides", Cherkassy, 1996 Etched in the specified rate of the seeds was tested on laboratory germination by seed in the coils by controlling the number of germinated seeds and counting the germination percentage. Then for seedlings after 14 days of growth was determined by the lengths of the stem and root systems is, then dried plant weight and were determined by dry weight of stems and seedlings compared with the control. Seeds were protravlivanie using dry etching with the flow : solution - 10-11 l/tonne of seed.

In table 4 shows the results of the experiments, according to which the patented structure increases the germination of seeds as compared with the prototype and comparison with the standard (the drug on the basis of tebuconazole Raxil, SK). At the same time patentable composition has a growth-stimulating effect in comparison with the prototype - drug based diniconazole and thiabendazole.

Table 4 The EFFECT of DISINFECTANTS ON CROP QUALITY, GROWTH AND DEVELOPMENT of BARLEY PLANTS
MEDICATION	Rate, l/t seed	Laboratory germination, %
Control, without processing	-	98	4/100	6/100
The preparation of the prototype	0,4	75	the 3.5/85	5,5/90
Composition 1	0,4	90	5,5/135	8,0/118
Part 2	0,4	94	5,9/148	8,5/128
Part 3	0,4	92	5,3/130	7,3/115
Part 4	0,4	96	5,6/136	7,6/116
Part 5	0,4	88	4,9/126	7,0/112
Part 6	0,4	90	5,2/133	8,0/117
Part 7	0,4	92	6,3/139	8,2/120
Part 8	0,4	85	5,3/135	7,4/114
Raxil	0,4	85	5,5/120	8,0/110

Example 5. Evaluation of biological activity against root rot and protection from diseases in field trials.

The experiments conducted on spring wheat (Sanita) and spring barley (variety Zasursky) in the Moscow region and the southern Piedmont area of Krasnodar Territory.

Bookmark and conduct experiments were conducted according to the "guidance on the state tests of fungicides, antibiotics and disinfectants seeds of agricultural crops", M, 1985, Seeds of wheat and barley were protravlivanie in : machine PS-10 with a consumption rate of solution : - 10 litres/ tonne of seed. Seeds were planted in the segment is Ah 10 m ². Control the degree of infestation of Fusarium and Helminthosporium the rot at different phases of development was carried out by digging 10% of the plants and to assess the degree of infestation of crops. After ripening was performed continuous manual cleaning of each plot and assessed the total yield of crops.

The results are presented in table 5 and 6.

It is established that the patented drug on the basis of tebuconazole and thiabendazole has a high degree of oppression, Helminthosporium and Fusarium rot on spring wheat and barley, and the introduction of thiabendazole in the drug significantly reduces the spread of rot Helminthosporium than one drug on the basis of tebuconazole - Raxil, Fri.

The effectiveness of dust suppression and particulate smut on wheat is 100%, the suppression of Fusarium root rot is 95-97%.

1. The composition for seed treatment in the form of a water-suspension concentrate containing as active substances the triazole fungicide range and 2-(4'-thiazolyl)benzimidazole (thiabendazole) (II), nonionic and anion active surfactants as wetting agent and dispersant, respectively, non, thickener, anti-freeze and dye, preservative, and water, characterized in that the triazole fungicide series composition contains (RS)-1-(4-chlorophenyl)-3-(1,2,4-triazole-1-yl-methyl)-4,4-dimethyl-pentane-3-ol (tebuconazole) (I), moreover, the ratio of the active substances I:II can vary from 20:1 to 1:20, as antifreeze - glycerine, or mixtures thereof with propylene glycol in a ratio of from 1:0.1 to 0.1:1, and further comprises a mineral or vegetable oil and the oil, which is used esters of phthalic acid, when the next General ratio of components, wt.%:

2. The composition for seed treatment according to claim 1, characterized in that the wetting agent contains at least one nonionic surfactant selected from the group of polyoxide the new and politprosveshenya fatty alcohols or alkyl phenols, including Nadasurf 860/R, Vitanol NP, Igepal SU 10 and OP-7 or OP-10, Neonol, and as a dispersant is at least one anion surface-active substance selected from the group of ammonium salts of di - or christiantamilringtonesj esters of phosphoric or sulfuric acids, including Suprior FL, Suprior 3D/33, Suprior 4D/384, Suprior BCA/7.

3. The composition for seed treatment according to claim 1, characterized in that as a thickener it contains a polysaccharide selected from the group Rhodopol 23, Bermocoll, carboxymethyl - or karboksimetilcelljuloza, and as a preservative of hexahydro-1,3,5-Tris(2-hydroxyethyl)symmetrizing.

4. The composition for seed treatment according to claim 1, characterized in that as lubricant it contains one of the esters of phthalic acid, such as DIPROPYLENE, dibutyl phthalate or dioctylphthalate, as a non - polydimethyl siloxane selected from Rodosil 426 and Penta 469, and as a dye, a cationic red 2C, or Varnish Rubin SC, or Lacquer ruby SC.

5. The composition for seed treatment according to claim 1, characterized in that the number of active of active ingredient in it is from 2 to 40 wt.%.

6. A method of combating plant diseases by pre-treatment of seed, wherein the seed is treated with an effective amount of a composition according to claims 1-5.