SK277835B6 - Fungistatic spraying 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

Technical field

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

BACKGROUND OF THE INVENTION

Substances used against the undesirable effects of various pests of plant and animal origin that damage plant cultures and the like are called pesticides. They are usually substances of an inorganic and organic nature, toxic to mammals and hence to humans or insect species which are directly desirable, such as e.g. bees. Therefore, their toxicity should be reduced to a minimum, whether by searching for new, less toxic or more effective substances, to be used at lower concentrations than previously known preparations, which are now widely produced and used in agriculture. At the same time, new plant diseases are emerging, against which the pesticides used so far have been ineffective or not at all effective.

These include diseases of cucumbers, but also other agricultural crops that have significantly reduced their fertility in recent years. It is a disease of fungal origin, manifested by spotting and drying of the leaves, leading to the chopping and extinction of the whole plant. Similarly, in the case of vines, besides common diseases such as peronospore, powdery mildew and the like, there is an increased disease of fungal origin, manifested not only by imperfect growth and unevenness of the berries in the bunch, but also by the drying of whole bunches. A similar situation, although 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 in the treatment of already infected crops, usually does not meet the expected success. also by using sprays containing substances of a toxic nature, especially at elevated concentrations. Thus, sprays are known [Meľnikov N. N .: Pesticides, Khimija, technologija i primeneňje, p. 111-113, 123-128, 668-674. Moscow, Khimiya (1987); Littig M .: Pesticide Manufactoring and Toxic Materials Control Enclyclopedia. Semitrailer Data Corporation. Rodge Park, New Yersley (1980); Cremlyn R .: Pesticides. Prague SNTL - Naklad. technical literature (1985) - based on copper salts (Kuprikol 50, Bordaux mixture), but also alkylphenols, chlorophenols, even alkyliphenol polyglycol ethers, but are few or even ineffective against many plant diseases, which is related to their structure, as well as inappropriate combinations of pesticides or potential pesticides. The present invention successfully solves these problems.

SUMMARY OF THE INVENTION

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. % of thymol and / or carvacrol in native form and / or at least partially water-soluble salts thereof, from 0.000002 to 0.002 wt. % of at least one triphenyl methane dye selected from fucsin, pyrocatechin violet, crystal violet, rhodamine B, thymolsulfophthalein, methyl green, malachite green, brilliant green and zinc salts thereof, and from 0.00005 to 0.5 wt. % anionic and / or nonionic surfactant and / or 0.00005 to 5 wt. copper salt.

The fungistatic spray mixture can also be prepared in 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 compound selected from sodium or calcium alkylbenzenesulfonate, the alkali metal salts of the higher C 10 -C 21 fatty acids and the partial esters of at least partially neutralized trihydrogen phosphoric acid organoesters with alkali metal hydroxides or triethanolamine.

The nonionic surfactant is selected from polyaddition products 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, polyaddition products of ethylene oxide to higher aliphatic amines, or carboxylic acids with an alkyl number of 8 to 22 , polyaddition products of ethylene oxide to alkanolamines and the addition or condensation of alkanolamines with higher carboxylic acids.

The preparation of a fungistatic 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 being dependent not on the order of addition of the individual components but on their final concentration. Advantageously, the above ingredients in native form can be formed into a hydroethanolic 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 potent fungistatic, growth-stimulant and growth-stimulant components. spray mixture. The most potent fungistatic components in the spray mixture are thymol (3-hydroxy-4-isopropyltoluene) and its isomer carvacrol (2-hydroxy-4-isopropyltoluene), belonging to the group of phenol derivatives which are still used as antiseptics in human medicine. .

Triphenylmethane dyes, which are also components of the spray mixture, in terms of their biological activity, can be classified as disinfectants, antiseptics, antifungals and anthelmitics, some of which have retained their practical importance as diagnostic dyes in human medicine for more than a century preparations, in the treatment of inflammation and mycoses or in the digestive tract deprivation of parasites, utilizing their anthelmintic properties over lower animal forms. The widespread use of the various properties of this class of compounds in other fields, such as cosmetics and food, guarantees the toxic safety of these components of the spray composition. Against this background, despite 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. However, experimental results indicate that the use of fucsi2

SK 277835 nu6 nu (Basic Fuchsin), pyrocatechin violet (gentian violet, pyrocatechin sulfophthalein), crystal violet (Basic Violet 3, methylrosalinine) of rhodamine B (Basic Violet 10, tetraethylrodamine) thymolsulfophthalein (thymol blue), methyl green 20 , malachite green (Basic Green 4), brilliant green and its zinc salt (Basic Green 1) as components of the fungistatic mixture as growth promoters are preferably because they promote photosynthesis. Their preservative properties against the overheating of the fruit (against the rotting of tomatoes and cucumbers) as well as the anthelmintic properties can also be used. However, their use as photosynthesis stimulators is very sensitive to their concentration. Their optimum concentration in the spray mixture results in a deepening of the green color of the leaves of the treated cultures within 5 to 30 minutes, which color is resistant to water (rain) washability. This suggests that some components react with the culture being treated. The pronounced insecticidal effects of triphenylmethane dyes to lower species of mammalian insects are manifested at their concentrations in the spray mixture, which represent the upper yet acceptable limit of their use as growth promoters. Therefore, the insecticidal properties of triphenylmethane dyes in the spray mixture should be evaluated only as marginal. The use of these substances at the optimum concentration results in an accelerated 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 triphenylmethane 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 adjust the surface tension between the spray composition and the tissue of the chemically treated culture. But with some surfactants such as e.g. alkylphenols, at their increased concentration in the spray mixture, may also adversely affect their increased biological activity, since far more effective fungicidal components are present in the spray mixture, such as possibly some of the above surfactants might be present, therefore it is sufficient to use lower concentrations thereof.

The described fungist spray mixture, which, like 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 and tested for a long time, and a combination with copper salts is particularly suitable where not only their synergistic effect, but also their combined effect can be observed.

The most potent fungistatic components in the spray mixture are thymol (3-hydroxy-4-isopropyltoluene) and its isomer carvacrol (2-hydroxy-4-isopropyltoluene) belonging to a group of phenol derivatives whose antimycoseptic properties in the field of human medicine have long been known. however, in native form, sparingly soluble in water. When copper ions are present in the solution, they react with them to form their copper salts, forming new types of compounds, their copper salts, characterized by higher biological activity and solubility than the original mixture of 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. If triphenylmethane dyes are present in the reaction system, copper salts of triphenylmethane dyes will also be formed as active fungistatic, growth-stimulating and anthelmintic components of the spray mixture; unreacted excess copper ions in the reaction mixture leads to a combined effect.

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

The advantage of the fungistatic spray composition according to the invention is its high fungicidal effect even in cases where it is applied to already affected crops, especially cucumbers, vines, tomatoes, apricots, peaches etc., the possibility of using extremely low concentrations including its use in the early spring. vegetation calmness, suitability for preventive, but also common treatment of cultures, technical availability of practically non-toxic ingredients and possibility of modification with other, long-time tested preparations, high resistance of spray against rain wash as well as long-term storage, disinfectant, conservative, anthelmintic and growth stimulation the effect as well as the relatively wide concentration range of the components in the spray mixture, where multiple use of higher concentrations of the components in the mixture usually does not result in damage to the cultures. Last but not least, the significant synergistic effect of the components of the ftingistatic spray mixture is advantageous.

The effects of the spray mixture and manifestations on different cultures are different. 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 lead to the whole tree drying up. The described fungistatic composition, especially when applied at rest time, 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 symptoms depend on the degree of infestation of the treated tree. The heavily infested, spongy, overgrown leaves already fall off after the first spraying, whereby the areas of the infested leaves dry and eventually fall out. However, on uninfested leaves and flowers, respectively. non-fallen fruit, the growth-stimulating properties of the spray are particularly effective when they grow faster and are larger, the latter of which, in the case of fallen leaves, accelerate the growth of new leaves, so that during the ripening period the trees give normal birth. There is no need to repeat the spray more than once at an interval of approximately 1 to 2 weeks. The same manifestations of spraying can be observed in the chemical treatment of apples, pears or roses infected with fungal diseases, with the difference that its efficiency is lower and therefore it is advisable to repeat the spraying 1 to 2 times within 5 to 10 days depending on the condition of the treated plant. and the crispness of apples and pears and for complete eradication of the disease, the spraying should be repeated 2-3 times. Also in chemical treatment of grapevine against various fungal diseases, peronospore, powdery mildew, etc., it is possible to observe much more uniform development of berries,

EN 277835 Β6 drying of bunches and growth of new offshoots. It should be noted, however, that the vines require more regular treatment, at least four times chemical spraying during the growing season, and the center of gravity should be shifted to the spring season, but may be chemically treated more frequently depending on the state of the crop and need. In the chemical treatment of apoplexia infested apricots, for which there is currently no sufficiently effective chemical agent that attacks especially young individuals and causes whole trees to die, the effectiveness of the spray depends on the presence and concentration of the triphenylmethane dye. More effective are those formulations in which the spray mixture has been prepared by concentrating the concentrate at an 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. However, in the treatment of apricots, a spray solution is also suitable for application to strains and branches, which is directly related to the mechanism of apoplexy spread. When using a spray for the chemical treatment of gooseberries and currants against American powdery mildew, the effectiveness of the spray is also linked to the presence of a selected triphenylmethane dye, which is intended to be a crystal or pyrocatechin violet. to prevent this disease by spraying on not yet challenged individuals or during a period of vegetative tranquility. Several years of attempts to chemically treat cucumbers against the cucumber peronospore for a long time resulting in substantially lower 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 in the months of April to June, the cucumbers and the condition of the stand are treated preventively, i. using approximately half the concentration of the individual components in the spray mixture at two to three week intervals, while it is advisable to shorten the individual spray intervals in June and increase the concentrations of the individual components in the spray mixture. By approximately mid-August, it is advisable to apply the spray every week or at intervals of three to five days. However, in the second half of August, which also depends on the weather, the intervals between individual sprayings can be extended again for up to three weeks. The effects of the spray mixture can also be seen in the fact that the birth rate of greenhouse cucumbers, in particular, is prolonged until the late autumn period, while wild cultures show the birth rate until the first frosts arrive, especially on newly grown offsprings, many of which prove a significant growth-stimulating effect. At the same time, the substantial retardation of the fruit maturation proves the conservative properties of the spray. A similar situation, but to a lesser extent in terms of resistance, can be observed in tomatoes. In the chemical treatment of peppers, which in addition to fungal diseases are often also attacked by mammalian insects, it is even possible to observe an increase in the birth rate.

A markedly positive, synergetic effect of the spray mixture even in the presence of ions was observed in the chemical treatment of onions, garlic, leeks, beans, carrots, parsley and potatoes.

DETAILED DESCRIPTION OF THE INVENTION

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 alkylbenzene sulfonate 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 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 0.0015 wt. % ammonium salt of thymol, 0.001 wt. % surfactant prepared on the basis of partial organoesters of trihydrogen phosphoric acid, 0.0007 wt. % pyrocatechin violet and 0.004 wt. copper (I) oxychloride.

Example 5

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. copper (I) oxychloride.

Example 6

A spray mixture applicable in a water-soluble form was prepared consisting of 0.015 wt. % ammonium salt of thymol, 0.01 wt. % surfactant prepared on the basis of partial organoesters of trihydrogenphosphoric acid, 0.002 wt. % of pyrocatechin violet and 0.04 wt. copper sulphate.

Example 7

A spray mixture applicable in a water-soluble form was prepared 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. copper (I) oxychloride.

Example 8

A spray mixture applicable as an emulsion in water was prepared, consisting of 0.006 wt. % thymol potassium salt, 0.01 wt. % of an emulsifier consisting of an equimolar mixture of sodium dodecylbenzenesulfonate and ammonium lauryl sulfate, 0.0001 wt. % of pyrocatechin violet and 0.05 wt. copper (I) oxychloride.

Example 9

The spray mixture of Example 4 was used for preventive 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 on vines which had already been attacked before spraying, the spread of which was also dependent on its habitat, and the symptoms were also manifested on cucumbers. With a comparable spray mixture but omitting the ammonium salt of thymol, the symptoms of peronospore appeared on the cucumbers, and the powdery mildew attacked the vine. With another comparable blend as in Example 4 but omitting cuprous oxychloride, the symptoms of peronospore also appeared on the cucumbers, and the powdery mildew clearly attacked the vine.

Example 10

The spray mixture of Example 6 was used to chemically treat grapevine, cucumber, rose, gooseberry, powdery mildew, currant peach and stroke apricot. For gooseberries and currants, a significant effect on the spread of the disease has been observed. On the other hand, on the other treated plant cultures it was possible to observe the cessation of the spread of the disease. the whole leaves have dried up and fallen away, with the rapid growth of new leaves being observed. On the apricots it was possible to observe a cessation of leaf wilting of whole branches, but the spraying had to be applied in three to one month cycles during the whole growing season. However, by omitting brilliant green and increasing the concentration of copper oxychloride from 0.008 wt. to 0.08% by weight, accelerated growth of the offshoots was not observed on the cucumbers and, moreover, they remained partially attacked by peronospore, and the curl of peaches subsided as well more slowly. The attacked branches of apricots dried up.

Example 11

The fungistatic spray mixture of Example 5 was used to chemically treat the strains of apple, pear, cherry and plum infested with mold during the vegetation period, 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. Applying the previously prepared mixtures and stirring them with an electric stirrer before use did not take effect until 8 weeks.

Example 12

The spray mixture of Example 7 was used for the chemical treatment of vines, apples, pears, plums, cherries, peaches, apricots, gooseberries, currants and roses during the vegetation period (before spring break). Spraying was applied once. At the beginning of the vegetation period, significantly fewer fungal and fungal diseases, powdery mildew and cases of apoplexy were observed on treated plants than on untreated plants. With the omission of copper oxychloride, the reduction in fungal disease was less noticeable.

Claims (5)

PATENT CLAIMS A fungicidal spray mixture applicable in the form of an aqueous solution, emulsion and / or dispersion, characterized in that it consists of 0.005 to 5% by weight. % of thymol and / or carvacrol in native form and / or at least partially water-soluble salts thereof, from 0.000002 to 0.002 wt. % of at least one triphenylmethane dye selected from fucsin, pyrocatechin violet, crystal violet, rhodamine B, thymolsulfophthalein, methyl green, malachite green, brilliant green and zinc salts thereof, from 0.00005 to 0.5 wt. % anionic and / or nonionic surfactant and / or from 0.00005 to 5 wt. 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 claim 1 and 2, characterized in that the copper salt is copper oxychloride and / or copper (II) sulphate. The fungicidal spray mixture according to claim 1 to 3, characterized in that the anionic surfactant is formed by at least one compound selected from sodium or calcium alkylbenzenesulfonate, the alkali salts of higher fatty acids C 0 to C 21, partial esters of at least partially neutralized organoesters of trihydrogen phosphate metal hydroxides. or triethanolamine. The fungicidal 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, polyaddition products of ethylene oxide. to higher aliphatic amines and / or carboxylic acids having 8 to 22 carbon atoms, polyaddition products of ethylene oxide to alkanolamines and addition and / or condensation of alkanolamines with higher carboxylic acids.