HU223092B1 - Inorganic contact fungicide composition with improved storability and high activity - Google Patents

Abstract

As active ingredients, the preparation contains sulfur and/or copper oxychloride and/or copper hydroxide, vegetable oil, vegetable lecithin and tetramethylthiuram disulfide mixed with emulsifiers and deionized water. ŕ

Description

FIELD OF THE INVENTION The present invention relates to an inorganic fungicidal composition having an environmentally friendly contact effect, which is sulfur and / or copper oxychloride [Cu ₂ Cl (OH) ₃ ] and / or copper hydroxide [Cu (OH) ₂ ] and a plant material having improved efficacy and storage life. oil, preferably sunflower and / or rapeseed oil, vegetable lecithin, preferably soya lecithin (in the form of a mixture with tetramethyltriuram disulfide).

It has been a long-standing effort to reduce the cost to farmers of the technological side of crop protection all over the world, so that the efficiency of treatment does not change or improve. Ionic and non-ionic adjuvants and mineral oil derivatives have been used in the development of intensive plant protection technology.

Aqueous oil emulsions were used to increase the efficacy of nicotine as early as the 30's (HGH Keams et al., Univ. Bristol Agr. Hort Research. Staff, Ann. Rept. 1932, 66-85).

Pesticides are mainly applied to the plants in the form of aqueous spray drops. The droplets of the meadow flake or peel off the surface of the leaf. The quick-drying coating remaining on the leaf adheres for a shorter or longer period of time and exerts its desired effect. The adherence of agents to the plant surface is promoted by water-soluble adhesion (sorption) agents.

Hungarian Patent No. 159,253, for example, uses an additive of naphthylsulfonic acid-formaldehyde complex and carboxymethylcellulose for this purpose.

In addition to the adhesive, emulsifiers are also used in the formulations to aid mixing with water. Thus, U.S. Patent No. 176,051 discloses an adjuvant oil comprising 55-95% by weight of a mineral oil, preferably a mixture of paraffin oil or petrolatum oil and 10% by weight of an emulsifier.

Mineral oil-based adjuvant oils are not used as an effective adjuvant for pesticides. Limited reasons for these applications include:

- Only emulsifiable oil formulations which do not cause phytotoxic symptoms should be used during the growing season. To eliminate the scorching effect, the aromatic and unsaturated parts of the mineral oil must be removed, which increases the price of the oil.

- In sunny days, preparations containing only saturated compounds can cause scorch by oxidising oils in the air to acidic compounds in the air and damaging the epidermis.

For reasons of environmental protection, European Community directives do not recommend preparations of mineral oil and ionic type or restrict the use of animal fat additives.

Lecithin in purified form is used by the cosmetics industry and human medicine as a rejuvenating agent, but the use of lecithin in the pesticides industry is not unknown either.

Hungarian Patent No. 171,456 discloses compositions for controlling wintering fungi which contain one or more surfactants, including lecithin, as the active ingredient. Lecithin is disclosed, inter alia, in EP 115 622; EP 009 503; EP 448,070; DE 3 686 953; U.S. Pat. No. 4,902,333; U.S. Patents 4,698,362. DE 309 765 discloses fungicidal combinations containing on the one hand a known fungicide and on the other hand a vegetable oil or lecithin or linoleic acid. The specification discloses lecithin as a substance used to reduce surface tension, optionally resulting in an increase in efficacy of lecithin fungicides administered in excess of the amount used to reduce surface tension.

(Tetramethylthiuram disulphide) (TMTD) is a known contact fungicide which is used primarily in agriculture for seed dressing.

The present invention is directed to a fungicidal composition in which an effective amount can be used to reduce the amount of active ingredients so that the compositions comply with the modem environmental regulations and reduce the environmental loading of chemicals.

It has been found that the use of ecologically and agronomically advantageous vegetable oil as a carrier in fungicidal compositions instead of refined mineral oil-derived adjuvants increases the efficacy of the fungicides without showing the adverse side effects of the mineral oils. The rate of improvement in efficacy ranged from 10-30%, i.e. with 10-30% less fungicide, the same biological effect could be achieved as with conventional formulations.

Vegetable oil is not an aliphatic hydrocarbon but a triglyceride, that is, glycerol esters of oil and fatty acids, where degradation can occur at the ester bond. The first product of hydrolysis is di-, monoglycerides, followed by glycerol and the liberated fatty acids or their salts. The two degradation products have no adverse effect on the plant or the environment as each of these substances is present in plants.

On the other hand, the oxidation of glycerol esterified esters of glycerol with unsaturated bonds may be a problem for the storage of some vegetable oil-based fungicides. Although oxidation does not affect the biological activity of the formulations, rancidity reduces the utility value of the formulation.

Although the use of various antioxidants to prevent rash is known in practice, in many cases, antioxidants may adversely affect the effect of the formulation or may be harmful to the environment.

It has now surprisingly been found that the use of mixtures of lecithin and tetramethylthiuram disulphide (TMTD) as antioxidants in each of the fungicidal compositions of the present invention may inhibit the effect of vegetable oil rancidity, and even the unexpected efficacy of the compositions. Efficiency gains can reach 60-80%.

This phenomenon is important in the field of environmental protection, since the amount of active ingredient of the sprayed pesticide can be reduced by one-third to one-fifth when using the compositions of the invention.

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The fungicide load on the environment is reduced, less fungicide is applied to the vegetation and, ultimately, less contaminated plant products are passed on to consumers.

Lecithin contributes to the emulsifiability and adhesion of the vegetable oil-based fungicides of the invention.

Lecithin is preferably of plant origin and generally does not require purification. A mixture of lecithin of plant origin and the corresponding oil may also be used as lecithin. Preferably, lecithin of the grade MSZ 08-1125 is used. The composition according to the invention comprises 10-70% by weight of sulfur and / or copper oxide chloride [Cu ₂ Cl (OH) ₃ ] and / or copper hydroxide [Cu (OH) ₂ ], 5-50% by weight of vegetable oil, preferably sunflower oil and / or rapeseed oil, rejuvenating, booster and antioxidant additives in an amount of 1 to 5% by weight vegetable lecithin or a mixture of lecithin and the appropriate oil, 2 to 10% by weight of a surfactant, which may be cationic, anionic or nonionic; a mixture of surfactants and containing 0.05-0.5% by weight of TMTD (tetramethylthiuram disulfide) and deionized water in a homogenized state.

Some formulations of the compositions of the present invention are described in the following examples.

Example 1: Sulfur 600 FW

Sulfur 60 parts by weight Sunflower oil 19 parts by weight Ion-exchanged water 16 parts by weight Supragil MNS / 90 (Rhone-P.) 1.3 parts by weight Soprophor FL (Rhone-P.) 3.2 parts by weight ethylene glycol 6.0 parts by weight Wessalon SV (Rhone-P.) 0.6 parts by weight Emulsion R.D. (Dow Corning) 1.3 parts by weight Lecithin 1.5 parts by weight Tensiofix XD 11 (Omnichem) 1.0 parts by weight TMTD 0.1 parts by weight Example 2: Sulfur 150 FW Sulfur 15.0 parts by weight ethylene glycol 2.1 parts by weight Supragil MNS / 90 (Rhone-P.) 0.6 parts by weight Soprophor FL (Rhone-P.) 0.9 parts by weight Tensiofix XD 11 (Omnichem) 5.0 parts by weight Emulsion R.D. (Dow Corning) 3.0 parts by weight Wessalon SV (Rhone-P.) 0.15 parts by weight Lecithin 1.5 parts by weight Silicone SRE 0.3 parts by weight formalin 0.03 parts by weight TMTD 0.05 parts by weight Sunflower oil 46.52 parts by weight Ion-exchanged water 24.85 parts by weight Example 3: Copper hydroxide 350FW Copper hydroxide 35.0 parts by weight Wessalon SV (Rhone-P.) 0.45 parts by weight propylene 3.6 parts by weight Tensiofix XD 12 (Omnichem) 1.5 parts by weight Tensiofix XD 11 (Omnichem) 2.0 parts by weight Lecithin 1.0 parts by weight

TMTD Emulsion R. D. (Dow Corning) Repceolaj Ion-exchanged water 0.05 parts 3.4 parts 28.0 parts 25.0 parts 25.0 Example 4: Copper oxychloride 600 FW Copper oxychloride 60.0 parts by weight Ultrasil VN3 1.1 parts by weight ethylene glycol 6.0 parts by weight Tensiofix XD 23 (Omnichem) 5.3 parts by weight Tensiofix XD 11 (Omnichem) 1.7 parts by weight Emulsion R.D. (Dow Corning) 1.3 parts by weight Lecithin 6.0 parts by weight TMTD 0.1 parts by weight Sunflower oil 5.0 parts by weight colza oil 5.0 parts by weight Ion-exchanged water 8.5 parts by weight Example 5: 650 W of copper sulfur Sulfur 45.0 parts by weight Copper hydroxide 20.0 parts by weight Soprophor FL (Rhone-P.) 3.0 parts by weight Supragil MNS / 90 (Rhone-P.) 2.0 parts by weight Tensiofix XD 11 (Omnichem) 1.2 parts by weight ethylene glycol 7.0 parts by weight Wessalon SV (Rhone-P.) 1.0 parts by weight Silicone SRE 1.0 parts by weight TMTD 0.1 parts by weight Lecithin 1.5 parts by weight colza oil 8.9 parts by weight Ion-exchanged water 9.3 parts by weight Example 6: Copper 150FW Copper oxychloride 15.0 parts by weight ethylene glycol 2.2 parts by weight Dispergiermittel LFS 0.8 parts by weight Supragil MNS / 90 0.5 parts by weight Emulsogen M 3.7 parts by weight Tensiofix 35300 (Omnichem) 2.65 parts by weight Wessalon SV (Rhone-P.) 0.2 parts by weight Lecithin 1.6 parts by weight TMTD 0.5 parts by weight Silicone SRE 0.3 parts by weight formalin 0.05 parts by weight Sunflower oil 46.0 parts by weight Ion-exchanged water 26.5 parts by weight Example 7

Hübl's iodine number is used to determine the rancidity of vegetable oils, from which stability can be inferred. The iodine number is the amount of iodine in grams that can be absorbed per 100 g of fat or oil under specified experimental conditions.

The pure oleic glycerol ester containing an unsaturated bond has an iodine number of 86.2. The glycerol ester of the linoleic acid containing two unsaturated bonds has an iodine number of about 260. Vegetable oils contain a mixture of different proportions of fatty acids, the proportion of which is affected by the place of production and the variety.

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As a result, for example, the iodine number of sunflower oil varies from 122 to 135, while that of rapeseed oil ranges from 97 to 105.

Iodine number László Erdei „Introduction to Chemical Analysis II.” (Textbook Publisher, Budapest, 1962, pp. 229-234).

The test compositions were placed in an open container thermostat and kept at 54 ° C for 4 weeks.

Thereafter, the iodine number was measured, indicating progression of rupture or loss of stability.

The synergism between antioxidants, which means more than the additive effect, can be calculated by the following formula (DL Richter, Pestic. Sci. 1987).

19. 4. 303-31S):

where:

H _a = the calculated additive effect,

_H = the effect of the material in%,

_Bh =% effect of substance B,

C = area outside the effect of substance A.

The formulation of Example 1 and variants thereof were tested.

The l / a. lecithin, while l / b. and TMTD was missing from the sample. Instead, deionized water was added to the samples, the other components of which were identical to those of Example 1.

Table 1

Variation of iodine number in samples of different composition

Example 1 l / a. Example 1B l / b. Example 1B 1. At the beginning of the test (absolute value) 125 128 131 2. At the end of the test (absolute value) 118 79 74 3. Measured relative% 2/1 94 63 56 4. Calculated relative% 78 - -

The results obtained illustrate that mixtures of the antioxidants of the present invention are more effective in inhibiting rancidity than the two antioxidants alone, which also indicates that the stability of the vegetable oil-based formulations can be enhanced by a mixture of lecithin and TMTD.

Example 8

The effect of the preparation of Example 3 on the onion peronospora was investigated in onions. The test was carried out on 10 m ² plots in 4 replicates with provocative infection of red onion onion. 40 Treatments VI. We started on the 14th and performed weekly on a weekly basis. 19th. Evaluations were performed before each spraying and two weeks after the last spraying, by bonitizing 50 plants per plot on a scale of 0-6 and calculating infection in30 dex.

scale Values Damaged lc surface% 1. Free 0 2. insignificant Below 6.2% 3. Weak 6.3 to 12.5% 4. medium 12.6 to 25.0% 5. Strong 25.1 to 50.0% 6. Very strong Above 50%

scale value

Infection index = Σ -: --— number of plants tested

Table 2

treatments The dose is 1 kg / ha Infection index VI. 14th VI. 21st VI. 27th VII. Third VII. 12th / 11th 19 VIII. Third Example 3 3.0 0.48 1.82 1.95 1.98 1.95 2.30 5.02 Champion 50 WP (Aqtrol Chem / USA) 3.0 0.47 1.70 1.86 1.91 2.06 2.42 5.47 Untreated control - 0.79 2.41 3.12 3.17 4.02 5.29 6.0

The results of this study show that the composition of the present invention having a copper hydroxide content of 35% by weight has approximately the same biological effect as Champion 50 WP (77% by weight copper copper hydroxide).

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Example 9

The effect of the composition of Example 1 on apple dew mildew was investigated in a 23-year-old Jonathan orchard with spindle cultivation.

The treatments were carried out at 7-14 days from the onset of the mouse (TV. 12.) to the beginning of fruit ripening (VIII. 23.).

The anti-mildew effect was evaluated on 10 leaves per 100 leaves per treatment (VI. 5; VIII. 30.). The percentage of infection on fruit was determined by examining 10 trees per treatment with a total of 500 fruits. Sulfur 900 FW (900 g / l sulfur) was used as a standard preparation in the assay.

Table 3

treatments Dose, 1 / ha I rating II. evaluation infection Infection% % index leaf fruit Example 1 vir. e. 3.0 vir. u. 2.0 11.0 1.53 13.0 4.0 Sulfur 900 FW (Budapest Chemical Works Co.) vir. e. 7.0 vir. u. 4.0 26.0 2.17 28.0 15.0 Untreated control - 97.0 3.79 100.0 100.0

vir. before flowering; vir. u. = after flowering

The effect of apple powdery mildew on the composition of the invention was lower than that of the standard composition, even at lower doses. The use of sulfur in so-called organic production can also be a problem if the amount of sulfur applied per hectare exceeds 4 kg per hectare. This problem is not to be considered when using the composition of the present invention as only 1.8 kg per hectare was used even at the highest dose of the composition.

Claims (9)

PATIENT INDIVIDUAL POINTS 1. An improved inorganic fungicidal composition with improved storage capacity and increased efficacy of 10-70% by weight of sulfur and / or copper oxychloride [Cu ₂ C (OH) 3] and / or copper hydroxide [Cu (OH)]. ₂ ], a surfactant and a carrier, wherein the composition is in the homogenized state as a 5-50% w / w vegetable oil, preferably sunflower and / or rapeseed oil, 1-5% w / w vegetable lecithin, 0.05-0.5% as antioxidant containing by weight of tetramethylthiuram disulfide, 2-10% by weight of surfactant and deionized water. Composition according to claim 1, characterized in that the composition comprises lecithin and tetramethylthiuram disulfide in a weight ratio of 100: (2-1). Composition according to claim 1, characterized in that the weight ratio of sulfur to copper compound (3-2) is: 1. 4. A composition according to claim 1, wherein the lecithin is a lecithin of plant quality, preferably of the type MSZ 08-1125, or a mixture of lecithin and the corresponding oil, preferably a mixture of soybean oil and soya lecithin. 5. The composition of claim 1, wherein the composition comprises a technical grade oil as a vegetable oil. 6. Use of a mixture of vegetable oil, plant lecithin and tetramethylthiuram disulfide to enhance the efficacy of a contacting fungicide composition comprising sulfur and / or copper oxychloride or copper hydroxide. Use according to claim 6, wherein the weight ratio of the mixture of vegetable oil, plant lecithin and tetramethylthiuram disulphide (5-50) :( 1-5) :( 0.05-0.5). Use according to claim 6, wherein the weight ratio of the mixture to the sulfur and / or copper compounds (5-50) is (10-70). Use according to claim 6, wherein the vegetable oil is sunflower oil and / or rapeseed oil.