CZ314588A3 - Fungicidally static spray mixture - Google Patents

Abstract

Fungistatic spraying mixture aplicable form of liquid solution or emulsion and/or suspension consists of 0,005 to 5 per cent weight of thymol and/or carvakrol in native form and/or of their at least partyl watersoluble salts with advantege of sodium and/or ammonium salts, next from 2.10/EXP -6/ to 2.10/EXP -3/ per cent weight at least one triphenylmethane dye chosen from among fuchsine, pyrocatechine violeti, crystaline violeti, rhodamine B, thymolsulphophthaleine, methyl green. Malachite green brilant green and from their zinc salts, from 5.10 exp.-5 to 5.10 exp.-1 per cent weight of anion and/or nonionic tenside and.or from 5.10 exp.-5 to 5 per cent weight of copper salt which is created by sulfate copper and/or oxychloride copper. Spraying mixture is usable in farming and forestry, mainly advantegeous in horticulture.

Description

Fungistatic spray mixture

The invention relates to a fungistatic spray mixture having a synergistic effect of its components, applicable in the form of an aqueous solution, emulsion and / or suspension mainly in agriculture for the chemical treatment of cultures against fungal and fungal diseases.

The various pests of plant and animal origin continually damage the cultures of flax growth, stocks of agricultural products, etc. Substances used to counteract these adverse effects by pesticides are classified according to their specific action. They are usually substances of an inorganic and organic nature, toxic to mammals and thus to humans, or to insect species which are directly desirable, such as bees. Therefore, their toxicity should be minimized, either by looking for new, less toxic pesticides, or more effective, usable at lower concentrations than known pesticides. Moreover, at the same time, new plant diseases are emerging, against which the pesticides used so far have been ineffective or even ineffective.

Such patrla cucumber disease, but also other agricultural cultures, which in recent years a substantial extent ^one limit their fertility. It is a disease of fungal origin, manifested by spotting and drying of the leaves, leading to drying and extinction of the whole plant. Similar to vines, besides common diseases such as perenospore, powdery mildew and the like, there is an increased occurrence of fungal origin, manifested not only by imperfect plant and unevenness of the berries in the tassel, but also by the drying of whole bunches. A similar situation, albeit not in the same intense form, is observed in various agricultural crops, and the application of industrial and recommended, very toxic pesticides based on inorganic or organic substances and their salts, in particular, usually does not meet the expected success. However, also using spraying with content

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substances of a toxic nature, in particular at elevated concentrations. Thus, sprays are known [Meínikov Ν. N .: Pesticides. Khimija, technologi i primeneni, pp. 111-113, 123-128, 668-74. Moscow, Khimija (1987); Littig M.: Pesticide Manufacturing and Toxic Materials Control Encyclopedia. Nav Data Corporation. Rodge Park, New Yersley (1980); Cremlyn R.: Pesticidy.Praha SNTL - Naklad. technical literature (1985) - based on copper salts (Kuprikol 50, Bordaux mixture), but also alkylphenols, chlorophenols, even alkylphenol polyglycol ethers, but they are few or even ineffective against many plant diseases, which is related to their structure as well as unsuitable combinations of pesticides or potential pesticides. However, the present invention successfully solves these problems.

The present invention is based on a fungistatic spray mixture which can be applied in the form of an aqueous solution, emulsion and / or dispersion, consisting of 0.005 to 5% by weight. % thymol and / or carvacrol in native form and / or at least a portion thereof of water-permeable salts, 0.000002 to 0.002 wt. % of at least one phenylmethane dye selected from fuchsin, pyrocatechin violet, crystal violet, rhodamine B, thymolsulfophthalein, methyl green, malachite green, brilliant green and their zinc salts, 0.00005 to 0.5 wt. % anionic and / or nonionic surfactant; , copper salt.

The fungistatic spray mixture can also be prepared so that the water-soluble salt of thymol or carvacrol is their salt, most preferably their sodium, potassium and ammonium salts.

The fungistatic spray mixture can also be prepared by adding a copper salt, in particular in the form of copper oxychloride, copper sulfate, or copper acetate.

The anionic surfactant comprises at least one of the boundary of sodium alkylbenzene sulphonate or phosphate, alkali metal salts of higher fatty acids ^C C 1Q.až partial esters with at least a portion neutrauzovaných organoesterov orthophosphoric acid. as alkali metal hydroxides or triethanolamine.

The nonionic surfactant is selected from the products of polyaddition of ethylene oxide to aliphatic alcohols having a carbon number of 10 to 21, or alkylphenols with alkyls having a carbon number of 8 to 18, &quot; r - 0X4? ¹ _: polyaddition products of ethylene oxide to higher aliphatic amines or carboxylic acids with alkyls of 8 to 22 carbons, polyaddition products of ethylene oxide to alkanolamines and addition or condensation of alkanolamines with higher carboxylic acids.

The preparation of a fungistatic spray mixture can also be carried out in such a way that any of the above-mentioned components can be prepared both separately and together, the resulting effect is not dependent on the order of addition of the individual components but on their final concentration. Advantageously, the above-mentioned components in native form form an aqueous-ethanol suspension which is concentrated or dried at a temperature of up to 80 ° C, resulting in the formation of copper salts of thymol, carvacrol and triphenylmethane dyes, as the most effective fungistatic, growth-stimulating agents. and the anhelmentic components of the spray mixture.

The most effective fungicidal components in the spray mixture are thymol (3-hydroxy-4-isopropiltoluene) and its isomer carvacrole (2-hydroxy-4-isopropyltoluene), belonging to the phenol derivative family which are still used as antiseptics in human medicine.

Triphenylmethane dyes, which are also components of the spray mixture, from the point of view of their biological activity, can be classified as disinfectants, antiseptics, antifungals and anhelmentics, some of whom have retained their practical importance in human medicine for more than a century pharmaceutical preparations, in the treatment of inflammations and mycoses, or even in the digestion, using their anthelytically lower animal forms. The widespread use of the various properties of this class of compounds in other fields, such as cosmetics and food, ensures the toxic safety of these components of the spray composition. Against this background, despite the different concentrations of triphenylmethane dyes which in the spray mixture must be several rows lower than in the above-mentioned application areas, their fungicidal effects could be expected. Experimental results, however, point out that the use of fuchsin (Basic Fuchsin), the pyrocatechin tract of parasites, properties compared to • K, ' ¹ ''''*>' ·. '* Ws - <>·'-> ^, -, - - », violet / gentian violet, pyrocatechin sulfophthalein /, crystal violet / Basic Violet 3, methyirosaniline /, rhodamine B / Basic Violet 10, tetraethylrodamine / thymolsulfophthaine / thymol blue /, methyl green / Basic Blue 20 /, malachite Basic Green 4, brilliant green and is zinc salt (Basic Green 1), as components of a fungistatic mixture in the interest of growth promoters by promoting foosynthesis. Their preservative properties against the overheating of the fruit (against the rotting of tomatoes and cucumbers), as well as the anhelmentic properties, can also be applied. However, their use in the form of photosynthesis stimulators is very sensitive to their concentration. Their optimum concentration in the spray mixture results in a deepening of the green coloration of the leaves of the treated cultures within 5 to 30 minutes, irrespective of the color of the triphenylmethane dye used. / rain /. This suggests that some components are reacting with the culture being treated. The pronounced insecticidal effects of triphenylmethane dyes to lower species of absorbent insects manifest at such concentrations in the spray mixture that represent the upper, yet viable limit of their use as growth promoters. Therefore, the insecticidal properties of triphenylmethane dyes in the needed mixture should be evaluated only as marginal. The use of these substances at the optimum concentration results in the rapid recovery of the newly growing offshoots on the treated culture, even if the lower growing part is already heavily attacked. It is further preferred that tri-nylmethane dyes alone are not toxic, but that they can be used as growth promoters at extremely low concentrations.

A further group of substances in the spray composition are surfactants which modify the surface tension between the spray composition and the tissue of the chemically treated culture. However, with some surfactants such as alkylphenols, at their increased concentration in the spray mixture, their increased biological activity may also be adversely affected; since more effective fungicidal components, such as any of the above surfactants, may be present in the spray mixture, it is sufficient to use lower concentrations thereof.

The fungistatle described spray mixture, which, similar to other types of pesticides, may have an even wider range of effects. It can also be modified with other types of spray mixtures that have been tried for a long time, and it is particularly suitable to combine with copper salts, where it is possible to observe not only their further enhanced synergistic effect, but also the combined effect.

The most effective. The phosphoic components in the spray mixture are thymo (3-hydroxy-4-isopropiltoene) and its isomer carvacro (2-hydroxy-4-isopropyltoluene) belonging to the group of phenol derivatives whose antimycoseptic properties in the field of human medicine have long been known but which are poorly water soluble in the natural form. If they are present in the solution, the copper ions react with them to form their copper salts and produce new types of compounds, their copper salts, characterized by higher biological activity and solubility than the original mixture of the components in the spray mixture. In practical application this results in an increased effect of the spray mixture, i.e. as a synergistic effect. By temperature, these equilibrium reactions can be accelerated. Therefore, it is also possible to form an aqueous-ethyl alcohol suspension from the above components in native form, which is concentrated or dried at a temperature of up to 80 ° C. This leads to the formation of thymium, carvacrol copper salts and, if triphenylmethane dyes are present in the reaction system, as well as the triphenylmethane dye copper salts as active fungistatic, growth-stimulating and anheimentic components of the spray mixture; the unreacted excess of copper ions in the reaction mixture. results in a combined effect.

The mixture acts in contact and its toxicity is limited by the concentration of copper salts, which can be 100 to 500 times lower than that of industrially used copper preparations.

The advantage of the fungistatic spray composition according to the invention is its high fungicidal effect even when applied to the crops already affected, in particular cucumbers, grapevines, tomatoes, apricots, peaches etc. Possibility of using extremely low concentrations, including its use in early spring period of vegetative dampness, suitability for preventive but also common

Kultur cultivation of cultures. Technical availability, while practically non-toxic components and the possibility of modification with other, long-term tested preparations. High spray resistance to rain wash as well as long-term storage, its disinfectant, conservative, anheimentic and growth-stimulating effect, as well as the relatively wide concentration range of the components in the spray mixture, but several times the use of higher concentrations damage to cultures. Last but not least, the significant synergistic effect of the components of the fungistatic spray mixture.

The effects of the spray mixture and manifestations in different cultures are spicy. They depend on the qualitative composition of the spray mixture and the quantitative representation of the individual components, the type of disease, but also the condition of the culture to be treated. In the chemical treatment of peaches against curliness, the use of spraying is particularly advantageous because peaches do not tolerate copper salt sprayings applied in the form of copper sulphate or copper oxychloride in the growing season to achieve an effect in sufficiently high concentrations. This relatively common disease usually results not only in the destruction of the entire crop, but can result in the entire tree drying out. The fungistatic composition described above, especially when applied during the vegetation period, causes the disease not to appear in the growing season, and can also be applied in the flowering period at the indicated concentration of solution. Its manifestations depend on the degree of infestation of the treated tree. Strong, infested, spongy-thickened leaves already fall off after the first spraying, whereby the areas of the infected leaves dry and eventually fall out. However, on uninfected leaves and flowers, respectively. non-fallen fruit, the growth-stimulating properties of spraying are particularly effective in that they are faster and larger, and the latter of the fallen leaves are characterized by accelerated growth of new leaves, so that very strong infested trees during both fruit and flood ripening provide normal birth. There is no need for repetition of the dipping more than once in an interval of about 1 to 2 weeks. The same manifestations of spraying can be observed in the chemical treatment of apple, pear or lipstick infected

fungi with the effect that its efficacy is lower and therefore spraying should be repeated 1 to 2 times within 5 to 10 days, depending on the condition of the plant being treated, while the spread of powdery mildew and chrastavictosti apple and pear to completely eradicate the disease; -3 times repeat. Also in the chemical treatment of grapevines against various fungal diseases, peronospore, powdery mildew and the like. it is possible to observe a more even development of the berries, to prevent the drying of the bunches and the growth of new offshoots. It should be noted, however, that the vines require more regular treatment, at least four chemical spraying during the growing season, and the center of gravity should be moved to spring, but depending on the state of the crop and the need may be chemically treated more often. In the chemical treatment of apricot-infected apricots, not only of which there is currently anything available! no sufficiently effective chemical agent that attacks especially young individuals and results in the death of whole trees, the effectiveness of the spraying depends on the presence and concentration of the triphenylmethane dye. More effective are those formulations in which the spray mixture was prepared by concentrating the concentrate at elevated temperature in the presence of copper ions. In the treatment of already infected individuals spraying should be repeated at least three weeks at intervals throughout the growing season. In the treatment of apricot spray solution, however, it is also appropriate to apply to strains and branches, which is directly related to the mechanism of spreading and apopiexia. When using a spray for the chemical treatment of gooseberries and currants against American powdery mildew, the effectiveness of the spray is also related to the presence of a selected triphenylmethane dye to be a crystalline or pyrocatechin vioil. unchallenged individuals or in a period of vegetation. Several years of attempts to chemically treat cucumbers against the cucumber peronospore, causing long-lasting substantial yields, have shown that the described spray mixture appears to be one of the most effective means against this disease. In the chemical treatment of cucumbers, it is appropriate to proceed in such a way that:

BW $ W months April to June, cucumbers and crop conditions are treated preventively, ie using approximately half the concentration of individual components in the spray mixture at two to three-week intervals, while in June it is advisable to shorten the individual intervals between sprayings and the individual spray concentrations blends increased. By approximately mid-August, it is advisable to apply the spray every week, or at intervals of three to 12 days. However, in the second half of August, which also depends on the weather, the intervals between individual sprayings can be extended again up to three weeks. The manifestations of the spray mixture can also be observed in that the birth rate of greenhouse cucumbers, in particular, is prolonged until the late autumn period, while the free growing cul- tures show birthing until the first frosts arrive and especially on newly-grown offshoots. At the same time, the substantial retardation of the fruit overheating proves conservatively the spray properties. A similar situation, but to a lesser extent in terms of resistance, can be observed with tomatoes. In the chemical treatment of peppers, which, in addition to fungal diseases, are also often attacked by sucking insects, it is even possible to observe a substantial increase in parenthood. It is also possible to use a higher concentration spray because apricots are less likely to damage healthy leaves than in other cultures, which appears to be contradictory in appearance, because in some cases even the appearance of healthy leaves using spray, they will erupt. However, after these leaves have been sprayed, there is no need to repeat them systematically throughout the growing season. This is manifested not only by preventing the spread of already developed diseases, but also by the immediate introduction of new flowers and subsequent ripening of the fruit.

Significantly no synergistic effect of the spray mixture even in the presence of copper ions was observed in the chemical treatment of onions, garlic, leeks, beans, carrots, parsley, and mash.

The following examples illustrate the invention.

ί & -, se

Example 1

A spray mixture applicable in the form of an aqueous dispersion consisting of 0.5 wt. % thymol in native form and 0.001 wt. an alkylbenzenesulfonate based surfactant.

Example 2

A spray mixture applicable in the form of an aqueous emulsion consisting of 0.5 wt. % of carvacrol in native form and 0.01 wt. a surfactant prepared by polyaddition of ethylene oxide to castor oil.

Example 3

A spray mixture applicable in a water-soluble form was prepared consisting of 0.05 wt. % ammonium salt of thymol, 0.0008 wt. % zinc salt of brilliant green, 0.01 wt. a surfactant prepared by polyaddition of ethylene oxide to castor oil.

Example 4

A spray mixture applicable in a water-soluble form was prepared, consisting of 0.05 wt. % ammonium salt of thymol, 0.01 wt. % surfactant prepared on the basis of partial organoesters of trihydrogen phosphate, 0.0008 wt. zinc salt of brilliant green.

Example 5

A spray mixture applicable in a water-soluble form was prepared consisting of 0.05 wt. % ammonium salt of thymol, 0.01 wt. % of a surfactant prepared on the basis of partial organoesters of trihydrogenphosphoric esters. zinc salt of brilliant green.

Example 6

A spray mixture applicable in water-soluble was prepared. % form consisting of 0.0015 wt. % ammonium salt of thymol, 0.001 wt. % surfactant prepared on the basis of partial organoesters of trihydrogen phosphate, 0.0007 wt. % pyrocatechin violet and 0.004 wt. copper oxychioride.

Example 7

A spray mixture applicable in a water-soluble form of 0.015% by weight was prepared. % ammonium salt of thymol, 0.01 wt. % surfactant prepared on the basis of partial organoesters of trihydrogenphosphoric ester; % of pyrocatechin violet and 0.04 wt. copper sulphate.

Example 8

A spray mixture applicable in a water-soluble form consisting of 0.003 wt. % ammonium salt of thymol, 0.004 wt. % surfactant prepared on the basis of partial organoesters of trihydrogenphosphoric acid, 0.0015 wt.

brilliant green and 0.008 wt. of copper oxychloride.

Example 9

A spray mixture applicable to i

% in water-soluble form consisting of 0.3 wt. % ammonium salt of thymol, 0.02 wt. % surfactant prepared by polyaddition of ethylene oxide to nonylphenol 0.005 wt. % of crystal violet and 0.3 wt. of copper oxychloride.

Example 10

A spray mixture applicable in the form of (

an emulsion in water consisting of 0.006% (by weight of thymol potassium salt, 0.01% by weight of an emulsifier consisting of an equimolar mixture, sodium dodecylbenzenesulfonate and ammonium lauryl sulfate, 0.0001% by weight of pyrocatechin violet and 0.05% by weight of water);

of copper oxychloride.

Example 11

A spray mixture applicable in a water-soluble form of 0.3% w / w was prepared. % ammonium salt of thymol, 0.02 wt. % surfactant prepared by polyaddition of ethylene oxide to nonylphenol 0.005 wt. % of crystal violet and 0.3 wt.

of copper oxychloride.

Example 12

The spray mixture of Example 6 was used to prevent 10

active chemical treatment of grapevine, cucumber, carrot, tomato, pepper, parsley, garlic and onion. Spraying was repeated every two to three weeks. Symptoms of powdery mildew occurred only in grapevines which had already been attacked before spraying, the spread of which was also dependent on its habitat, and symptoms also occurred in cucumbers. With a comparable spray mixture but omitting the ammonium salt of thymol, prenospore symptoms manifested in cucumbers and powdery mildew attacked the grapevine. With another comparable composition to that of Example 6, but by omitting copper oxychloride, the symptoms of perenospore also appeared on the cucumbers, and the powdery mildew clearly attacked the grapevine.

Example 13

The spray mixture of Example 8 was applied to chemical roses, gooseberries, currants infested with curl, gooseberries and currants or to treat grapevines, cucumbers infested with powdery mildew, peaches and apricot infestations. U observed a significant impact on the spread of the disease. On the other hand, in the other treated plant cultures, the spread of the disease was observed, whereas in grapevines and cucumbers boio observed accelerated growth of new offshoots, in peaches and roses the strong infected part of the leaves, respectively. the whole leaves have dried up and fallen off while observing the rapid growth of new leaves. In Marhui, it was observed to stop the wilting of leaves of whole branches, but the shot had to be applied in three-week to monthly cycles throughout the growing season. However, by omitting brilliant green and increasing the concentration of copper oxychloride from 0.008% by weight. to 0.08 wt. the cucumbers did not exhibit accelerated growth of the offshoots and, moreover, they remained partially attacked by perenospore, and the curl of peaches subsided as well. The attacked branches of the apricots dried up.

Example 14

The spray mixture of Example 11 was used for the chemical treatment of vines, roses, cucumbers, carrots, tomatoes, peppers, parsley, garlic bulbs, potatoes, apples, pears, peaches, apricots, potatoes, gooseberries and currants. The spray mixture substantially limited the spread of the peronospore to

it prevented the bunches from drying out and the sugaring of the berry and caused even berry development on its bunches, while also promoting the growth of new offshoots. The spray solution further reduced the spread of the cucumber perenospore to a substantial extent, fed the birth rate of the freely growing cucumbers until mid-September, and the greenhouse cucumber's birthplaces susceptible until mid-October, depending on climatic conditions. No infection was observed in tomatoes and peppers during the growing season, and the later birth of dry dry tomatoes shifted to the arrival of the first frosts, and after application of the pepper spray, not only the introduction of new fruits, the prevention of fungal diseases but and the high birth rate of free growing cultures was prolonged until the arrival of frost. The parsley and carrots were not observed to dry out and they could be kept until the arrival of frost, while the freely left individuals in the following growing season could be used as early. When mildly attacked by fungi, this fungistatic spray was liquidated and their function restored. the strong invaded spots of the leaves dropped out after drying but the function of the other parts of the leaves was restored. Apple leaves have also withered or have been free from infection, but the fruit's crispness has diminished, as in pears, although the situation in these cultures is complicated by the possible presence of overlapping systemic diseases. The American powdery mildew and currants also retreated. The apricot stroke also stopped, so that withered leaves of thick infested branches of branches did not recover, but slightly infested branches of branches resumed their function, and against further spread the fungistatic spray mixture had to be repeated at three-week to one-month intervals throughout the vegetation period. period. In some treated crops, spraying was only necessary once (apple, pear), but in others, such as vines and cucumbers, it was necessary to use it more often in the growing season and the condition of the plants to be treated, but most often at three to weekly intervals. .

Claims (5)

Patent claims A fungistatic spray mixture, which can be applied in the form of an aqueous solution, an emulsion and / or a dispersion, characterized in that it consists of 0.005 to 5% by weight. % of tymphyl and / or carvacrol in the natural form and / or at least part thereof of water-soluble salts, 0.000002 to 0.002 wt. % of at least one triphenylmethane dye selected from fuchsin, pyrocatechin violet, crystal violet, rhodamine B, thymolsulfophthalein, methyl green, malachite green, brilliant green and their zinc salts, 0.00005 to 0.5 wt. % anionic and / or nonionic surfactant; copper salt. Fungistatic spray mixture according to claim 1, characterized in that the water-soluble salt of thymol and / or carvacrole is their alkali salts, preferably sodium salts and / or ammonium salts. Fungistatic spray mixture according to claims 1 and 2, characterized in that the copper salt is copper oxychloride and / or copper sulphate. The fungicidal spray mixture according to claim 1 to 3, characterized in that the anionic surfactant is at least one of sodium or calcium alkylbenzenesulphonate, the alkali salts of higher fatty acids C 2 to C _2J , partially esters with at least some of the neutralized organoesters of trihydrogen phosphoric acid, such as hydroxide. alkali metals or triethanolamines. Fungistatic spray mixture according to claims 1 to 4, characterized in that the nonionic surfactant is selected from polyaddition products of ethylene oxide to aliphatic alcohols having a carbon number of 10 to 21 and / or alkylphenols with alkyls having a carbon number of 8 to 18, produced in the polyaddition. ethylene oxide to higher aliphatic amines and / or carboxylic acids, with alkyls of 8 to 22 carbons, polyaddition products of ethylene oxide to alkanolamines, and Example 15 The fungistatic spray mixture of Example 8 was used for the chemical treatment of apple, pear, cherry and plum infested plants during the growing season, with the mixture being applied by brush. After spraying twice over 14 days, the mold was discarded. However, by omitting the surfactant and increasing the copper oxychloride to 0.01 wt. the effect did not appear until after five coats of freshly prepared spray mixture. When applying the scores of the prepared mixtures and mixing them with an electric stirrer before use, the effect did not appear until after 8 weeks. Example 16 The spray mixture of Example 7 was used for chemical treatment of vines, apples, pears, plums, cherries, peaches, gooseberry apricots, currants and roses during the vegetation period (for spring break). Spraying was applied once. At the beginning of the vegetation period, there was a significantly lower incidence of fungal and fungal diseases, powdery mildew and apoplexy in treated plants than in untreated plants. With the omission of copper oxyoxide, the reduction in fungal disease was less noticeable. addition and / or condensation of alkanolanones with higher xylic acids.