RU2240002C1 - Combined pesticide preparation and method for control plants disease and pest in plants - Google Patents

Abstract

FIELD: agriculture, pesticides.

SUBSTANCE: invention proposes a pesticide preparation used for control of diseases and pests in plants that comprises copper oxychloride as an active substance and concentrate of sulfite-alcoholic distillery grains or sulfite-yeast mash as a disperser representing an aqueous-suspension concentrate with size of solid particles 2-4 mcm. The preparation comprises additionally sulfur as an active substance and non-ionogenic surface-active substance, carboxymethylcellulose and water in the following ratio of components, wt.-%: colloidal sulfur, 27-40; copper oxychloride, 8-15; sulfite-alcoholic distillery grains or sulfite-yeast mash, 2.0-4.0; non-ionogenic surface-active substance, 0.5-2.0; carboxymethylcellulose sodium salt as 5% solution, 18-20; water, up to 100. Also, invention relates to a method for control of diseases and pests in plants by their treatment with the above described preparation. Invention provides enhancing effectiveness of effect the preparation.

EFFECT: improved method for control, valuable agricultural properties of preparation.

9 cl, 6 tbl, 1 dwg, 7 ex

Description

The invention relates to chemical plant protection products, namely to a combined pesticidal preparation containing sulfur and copper chloride as active components.

Both sulfur and copper oxychloride have long been widely used to combat fungal diseases of plants and herbivorous mites (see NN Melnikov et al. Handbook “Pesticides and Plant Growth Regulators”, pp. 311 and 418, - M .: Chemistry, 1995).

The most common formulations are wettable powders, pastes, dusts. Precipitated colloidal sulfur released during the purification of coke and other gases is also used.

The consumption of colloidal sulfur or sulfur in the form of a wettable powder for combating plant diseases and ticks is from 4 to 15 kg / ha, depending on the crop and the object to be destroyed.

In accordance with the current standard (TU-113-04-322-00), colloidal sulfur contains 75% sulfur and not more than 25% moisture.

Copper chloride is used to combat diseases of fruit, berry and vegetable crops at consumption rates of 1.6-7.2 kg / ha. The most common formulation is a wettable powder, which, in addition to the main active substance, contains a sulfite-alcohol stillage disperse concentrate (SSB) or sulfite-yeast mash (SDB) - 6-8%, as well as a small amount of impurities and moisture GOST 13200- 75 and N.N. Melnikov. Pesticides, chemistry, technology and application. - M .: Chemistry, 1987, p. 667).

A large number of combined preparations are known that contain copper oxychloride as one of the components, such as polychome (polycarbocin + copper oxychloride), chomecin (copper oxychloride + cyneb) and others, as well as mixtures of sulfur with other fungicides, for example, serocin (sulfur cineb) (see, for example, N.M. Golyshin “Fungicides”, - M .: Kolos, 1993 and the Catalog “Chemical means of plant protection”, Cherkasy, 1988).

Also known is the drug, which is prepared by the joint grinding of colloidal sulfur (75%) and zinc salicylanilide (25%) ed. testimonial. USSR No. 138113, A 01 N 59/02, 1961. As a rule, these mixed preparations are made in the form of wettable powders.

It is known to use a tank mixture of wettable powders of sulfur and copper chloride in a ratio of 5: 1 (N.M. Golyshin “Fungicides”, - M .: Kolos, 1993). In addition, in the directory “European Direktory of Agrochemical Products” V.L. “Fungicides” Third Edition, the Royal Society of Chemistry, 1988 contains information on combined preparations based on copper and sulfur chlorides that are produced and sold in various European countries, for example, Zwamdood, a wettable powder containing 20% chloroxide copper and 40% sulfur, the preparation “Cupromix” (20% HOM + 34% sulfur) and others recommended as a means to combat diseases of fruit, berry crops, tomatoes, potatoes, etc.

The recipes of these combined preparations are not given in the cited source, however, it is known that wettable powders, in addition to the active substances, contain a filler, dispersant and, possibly, an adhesive. In the case of a mixture of sulfur and copper oxychloride, the active substances themselves play the role of a filler, and dispersants can be very diverse, including those indicated in the formulation of a wettable copper oxychloride powder, i.e. PRS or RDS (see above, as well as N. N. Melnikov “Pesticides, chemistry, technology and application”, - M .: Chemistry, 1987, p. 34). Thus, the closest analogue of the combination preparation in accordance with the present invention is a combination preparation containing sulfur and copper chloride as active ingredients in the form of a wettable powder.

The disadvantages of these formulations are that they dust, cake, or coalesce to form large aggregates, have low dispersion and suspension stability, and have low particle adhesion on the surface of the treated plants, which leads to a decrease in the effectiveness of the drugs on pathogens and plant pests.

The objects of the present invention are a new formulation — a suspension concentrate — based on sulfur and copper oxychloride with improved physicochemical and consumer properties and greater effectiveness, as well as a method for controlling diseases and plant pests using this combined suspension preparation.

The combined suspension preparation in accordance with the present invention contains the following components in wt.%.

1. Sulfur colloidal 27-40

2. Copper oxychloride (HOM) 8-15

3. Sulphite-alcohol stillage (PRS) or

Sulphite-yeast mash (SDB) 2.0-4.0

4. Nonionic surfactant

substance (OP-7, OP-10) or Neonol AF 9-10 0.5-2.0

5. Carboxymethyl cellulose, Na-salt

(CMC) -5% solution 18-20

6. Propylene glycol or

Ethylene Glycol 0- (0-8)

7. Defoamer (silicone) 0-0.5

8. Anti-vaporizer AI-4P 0-3.0

9. Water up to 100

SSB or SDB are used as a dispersing and stabilizing substance, OP-7 and other non-inorganic surfactants are used as a stabilizer, CMC is used as a thickener to improve storage conditions, and ethylene glycol is used to improve the storage of the drug at low temperatures or propylene glycol, antifoam (silicone) is used to reduce the formation of foam.

The preparation is obtained by mixing and finely grinding all the components (or in parts) in an aqueous medium on a homogenizer, on a ball or bead mill.

After grinding and homogenization, a suspension concentrate is formed, which is stable during storage, with high physicochemical properties: particle _size (d _{cf. sound} ) is 2-4 microns; the stability of a 1% aqueous suspension of 85-92%; the specific surface area of the particles is S beats. = 24000-26000 cm ² / g; the pH of a 1% aqueous suspension of 6-7, the bulk density of the drug is 1.2-1.25 g / cm ³ .

As a stabilizer of the suspension, which allows to increase the shelf life of the drug and improve the quality of the suspension when spraying in the formulation, up to 3% of the AI-4P anti-evaporator can be added, which is a mixture of high molecular weight synthetic fatty alcohols of the C8-C18 or C10-C20 fraction with non-ionic surfactant OP- 7 (author's certificate. No. 333913, BI No. 12, 1972).

In addition to the preparation, a preservative may also be added, for example, formaldehyde in the form of a 10% aqueous-alcoholic solution.

In terms of biological activity, the new combined suspension preparation is superior to both individual components taken in the same concentration and a wettable powder containing sulfur and copper oxychloride taken in the same proportions and amounts as active substances. As experiments have shown, after storage for 6.5 months, the drug has remained highly effective against plant diseases and against spider mites. The physicochemical properties also remained unchanged, which could not have been assumed in advance, since there is no information on combined chemical preparations based on copper and sulfur chlorides containing water, their chemical and physical stability in the sources available, and the interaction of the individual components of the drug is different. with another in the aquatic environment, leading to a change in physicochemical properties and, as a consequence, to a decrease in biological activity, could not be excluded.

The new combined suspension preparation has a wide spectrum of action, combining the action spectra of its components, and exceeds technical standards, including on potatoes against late blight, 15-20%, on currants against powdery mildew, by 25-30%, and against ticks - by 40-45%.

The drug has a higher retention on the surface of plants compared with ChOM, due mainly to a high degree of dispersion and a high specific surface area of the particles of active substances, as well as the introduction of such components as KMTSiAI-4P into the formulation.

Improved adhesion is an important factor contributing to the improvement of the technical effectiveness of the drug, since it has a contact effect.

The suspension preparation is packaged in a double sealed polyethylene (film 150-180 microns) packaging in the form of small dosed sachets, which are very convenient for use in personal subsidiary plots, gardens, vegetable gardens. In this package, the drug can withstand storage for more than 6.5 months at a temperature of + 25 ° - + 35 ° C, without changing its properties, can also withstand storage at a temperature of -10 ° C - -15 ° C for at least 30 days.

The high efficiency of the suspension preparation made it possible to almost halve the consumption rate compared to the standards and thus reduce the cost of processing plants to combat diseases and pests, and make it environmentally safer.

The ratio of active substances (HOM: Sulfur) in the preparation can vary from 1: 2 to 1: 4, and their total amount is in the range of 40-50 wt.%.

For processing plants, the drug is diluted with water to obtain a suspension containing 0.4-0.8% of the drug.

When the ratio of Sulfur: XOM = 2: 1, the active substances are taken in the following amounts by AI

Colloidal sulfur 27-30%

HOM 13.5-15%

With a ratio of 3: 1

Colloidal sulfur 30-36%

HOM 10-12%

With a ratio of 4: 1

Colloidal sulfur 32-40%

HOM 8-10%

Auxiliary components for all three options may vary as indicated in the above composition of the combined suspension preparation.

Example 1. Getting the drug.

Colloidal sulfur and a 90% wettable powder of copper oxychloride are mixed in a ratio of 2: 1, 3: 1 and 4: 1 for the active substance in such quantities that the total content of the mixture for the active substance is, respectively, wt.%: 40.5- 45, 40-48 and 40-50. Separately, the calculated amount of surfactant (OP-7 or OP-10 or Neonol) and CSP (or SDB) are mixed, diluted in the calculated amount of water and mixed with a stirrer. All components are mixed, homogenized and ground in a ball or bead mill to achieve a particle size of 2-4 microns (30-40 minutes). The temperature of mixing and grinding of the components is maintained up to + 30 ° С, + 35 ° С. Then, a 5% aqueous solution of the Na salt of carboxymethyl cellulose is added to the resulting mixture, and the whole mixture is again homogenized for 15-20 minutes.

Antifreeze - ethylene glycol or propylene glycol in the amount of 5-8 wt.%, Silicone antifoam up to 0.5 wt.%, Anti-evaporator - up to 3.0 wt.%, As well as a preservative can be added to the resulting mixture. All additional components are thoroughly mixed with the main composition.

Samples containing antifreeze do not freeze at t = -10, -15 ° C for 30 days.

Sample No. 3, which did not contain antifreeze, froze at this temperature, but after thawing at room temperature it retained its physicochemical parameters.

The compositions of the samples of the preparations obtained are presented in table No. 1.

Example 2. Determination of the stability of an aqueous suspension.

The stability of suspensions was determined on a universal device UPOS - 2. The stability indices Kτ% over time τ were calculated by the formula:

where Po is the weight of the float in water, in grams;

 P1 - weight of the float in suspension before settling, in grams;

 Pτ is the weight of the float in suspension after settling, in grams by the time t (GOST 16484).

According to international standards, τ = 30 min.

The results are presented in table No. 2 and in the drawing.

From the results obtained it can be seen that the stability of the aqueous suspension of the new drug significantly exceeds the standards, as well as the standard value (80%) determined for suspension concentrates according to GOST R51247-99 “Pesticides” (general technical conditions).

Example 3. Determination of the degree of dispersion and specific surface.

The determination was carried out by the method of sedimentometric analysis according to the particle size distribution curves. Control analyzes were performed using a high resolution optical microscope.

The weighted average particle diameter was calculated by the formula:

where di is the average size of individual fractions in microns;

Δmi is the content of these fractions in the preparation in fractions of a unit.

The degree of dispersion (particle size) is in the range of 2-4 microns. The specific surface S _{beats was} calculated by the formula:

where di and Δmi have the above meaning, and ρ _tv.f. - the density of the solid phase of the drug in g / cm ³ (see V.P. Tropin et al. Collection “Chemical plant protection products”, issue 4, Moscow, 1973, p. 24).

The results for individual samples are presented in table No. 2

Example No. 4. Determination of the degree of retention (adhesion) of drugs.

Test specimens were sprayed onto standard glass plates coated with wax. After drying, they were weighed at room temperature. Then the plates, with the preparations applied on them, were placed in a special sprinkler, in which they were for 10-15 minutes. The difference in the weight of the plates before and after sprinkling was determined% retention. The results are presented in table No. 2.

As can be seen from the table, the highest adhesion is 85-90% in suspension concentrate (sample No. 9) with a degree of dispersion d _av.vzv. = 2.5 μm and specific surface area S _beats. = 26000 cm ² / g. The lowest is colloidal sulfur with a degree of dispersion d _avg. = 1500-2000 microns.

The table also shows that the pH value of 1% aqueous suspensions for all preparations is almost the same, that is, for a suspension concentrate, this indicator is the same as for the standards.

This indicates the absence of any chemical interaction between the components of the combined drug.

On the other hand, a pH value of 6–7 indicates neutrality of the medium, which determines the absence of phytotoxicity when processing green plants.

Example 5. Assessment of the biological activity of a new suspension preparation in greenhouse conditions.

The tests were carried out in the greenhouses “Fir-trees” of the Domodedovo district of the Moscow region on flower crops (roses, carnations, chrysanthemums, feces) in the summer-autumn period of 2002 by a double treatment method in accordance with the timing of the occurrence of the main diseases and spider mites.

Before preparing working suspensions, experimental samples, packaged in 40 g each, were manually mixed in plastic bags, transferred to containers with a small amount of water, mixed, and then diluted with water to obtain a suspension of the desired concentration.

The plants were treated using a manual sprayer at a liquid flow rate of 0.5 l per 10 m ² twice: the first time when diseases and ticks appeared, even before the appearance of colored buds, the second time after 10-12 days. On callas before rhizome separation, diseased rhizomes were cleaned of bacterial decay and soaked in test suspensions for three hours, and then planted in pots. When the first signs of septoria, alteriosis and ascochitosis appeared, plants were sprayed.

The biological effectiveness was taken into account during the flowering period according to the output of marketable products, the amount of which corresponds to the total efficiency of the suppression of plant diseases and spider mites by the test preparations. The test results are presented in table No. 3.

The synergy coefficient calculated using the indicators of this table according to the Colby formula for a new suspension preparation with a component ratio of 4: 1 is in the range of 1.50-1.89 relative units, that is, the activity of the drug significantly exceeds the total activity.

The calculation was carried out according to the Colby formula used to determine the additivity coefficients, and the results are shown in table 7.

where E is the efficiency in%, C is the concentration in%, A is sulfur; B - chrome; C _A = 80%; With _B = 20%.

Calculation example (according to the calculation rate of 40 g / 10 l)

Thus, K.S. for a suspension preparation in a ratio of 4: 1 is in the range of 1.50-1.89 relative units.

Example 6. Comparative tests of a suspension preparation on flower crops in greenhouses.

In the conditions of example 5, comparative tests of a new suspension preparation and a wettable powder containing sulfur and copper chloride as active substances in the same amounts as the suspension preparation were carried out, as well as tests of the suspension preparation after storage for 6.5 months at t = + 25 ° C - 35 ° C. The test results are presented in table No. 4.

Example 7. Tests of a new combined suspension preparation in the field.

The tests were carried out in areas of the horticultural partnership “Agrochemist” in the Domodedovo district of the Moscow Region against late blight on potatoes and against powdery mildew and spider mites on black and red currants. As a reference on potato against late blight, 90% wettable copper chloride powder was used, and colloidal sulfur on powdery mildew and ticks.

The tests were carried out with double treatment with an interval of 7-10 days. The potato cultivar used Zhukovsky early in the 18–20 leaf phase; on blackcurrant - varieties “Seedling Doves”, “Riddle”, on redcurrant - “Natalie”, “Chulkovskaya”.

Before preparing the working suspensions, the preparations were slightly mixed manually in the package, then transferred to a container, where concentrated 0.8% suspensions were first prepared. Then half the volume of the suspension was diluted in water to a concentration of 0.4%. All suspensions were uniform and stable. In the same way, suspensions were prepared from reference preparations. Spraying was carried out from a manual sprayer with a flow rate of 0.5 l / 10 m ² (potatoes) and 1 liter per bush.

The test results are presented in tables No. 5 and No. 6.

Tests have shown that suspension preparations by technical efficiency significantly exceed the standards. All samples have high consumer properties, are easy to handle and have a wide range of biological activity.

Tests have shown that Suspension Concentrate, both before and after storage, significantly exceeds wettable powder in terms of its effectiveness against diseases and spider mites.

Claims (9)

1. The combined pesticidal preparation for combating plant diseases and pests, containing copper chloride as an active substance and a sulfite-alcohol stillage concentrate (SSB) or sulfite-yeast mash, as a dispersant, characterized in that it is a water-suspension concentrate with a particle size of 2-4 microns and additionally contains sulfur as an active substance, as well as a nonionic surfactant, carboxymethyl cellulose and water in the following ratio of components in weight.%: Colloidal sulfur 27-40 Copper Chloride 8-15 Sulphite-alcohol bard (PRS) or Sulphite-yeast mash (SDB) 2.0-4.0 Nonionic surfactant 0.5-2.0 Carboxymethyl cellulose Na-salt, 5% solution 18-20 Water Up to 100 2. The combined preparation for combating plant diseases and pests according to claim 1, characterized in that it further comprises propylene glycol or ethylene glycol in an amount of 5-8 wt.%. 3. The combined preparation according to claim 1 or 2, characterized in that it further comprises a silicone antifoam in an amount of not more than 0.5 wt.%. 4. The combined preparation according to claim 1 or 2, characterized in that it further comprises an AI-4P anti-evaporator, which is a mixture of high molecular weight synthetic fatty alcohol fractions C ₈ -C ₁₈ or C ₁₀ -C ₂₀ with a nonionic surfactant, in an amount of not more than 3.0 wt.%. 5. The combined preparation according to claim 3, characterized in that it further comprises an AI-4P anti-evaporator, which is a mixture of high molecular weight synthetic fatty alcohols of the fraction C ₈ -C ₁₈ or C ₁₀ -C ₂₀ with a nonionic surfactant, in an amount of not more than 3, 0 wt.%. 6. The combined preparation according to claim 1 or 2, characterized in that the amounts of active substances in it — sulfur and copper chloroxide — are in the ratios (2-4): 1, respectively. 7. The combined preparation according to claim 3, characterized in that the amounts of active substances in it — sulfur and copper chloroxide — are in the ratios (2 ÷ 4): 1, respectively. 8. The combined preparation according to claim 4, characterized in that the amounts of active substances in it — sulfur and copper chloroxide — are in the ratios (2 ÷ 4): 1, respectively. 9. A method of combating diseases and pests of plants by treating them with drugs, characterized in that they use the combined preparation according to any one of claims 1 to 8, which treat plants in effective amounts, depending on the degree of their defeat by diseases and pests.