SK314588A3 - 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 fungistically sprayed composition with the synergistic effect of its components, applicable in the form of an aqueous solution, emulsion and / or suspension, especially in agriculture, chemical treatment of cultures against fungi and fungal diseases.

Description of the state of the art

Substances used against the undesirable effects of various pests of plant and animal origin that damage plant cultures and the like are called pescltifly. They are usually substances of an inorganic and organic nature, toxic to mammals and hence also to humans or to types of lunyza which are directly desirable, such as e.g. bees. Therefore, their toxicity should be reduced to a minimum by looking for new, less toxic or more effective substances, to be used at lower concentrations than the 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, which have significantly reduced their fertility in recent years. It is a disease of fungal origin, manifested by spotting and leaf drying, leading to drying and extinction of the whole plant. Similarly, in vine, in addition to common diseases such as perenospore, 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, a point not in the same intensive form, is observable in various agricultural crops, with the application of industrial and recommended, many times oxen, toxic post-based substances to inorganic or organic substances and salts, especially in the treatment of already infected crops with the expected success of using sprays containing substances of a toxic nature, especially at elevated concentrations. Thus, C. Meínlkov N.N.

Pesticides. Khimija, tochnologlja 1 prlmeneňje, p. 111 - 113

123-128, 668-74. Moscow, Khimiya (1987); Littig M .: Pestlci.de

Manufacturing and Toxin Materials Control Fncyclopedia. Semitrailer Data Corporation. Park Rodge, New Yorsloy (1980); Cremlyn R .: Pesticides.Praha SNTL - Nakl ad. Copper salt 60 (Kuprikol 60, Bordaux mixture), but also alkylphenol, chlorophenols, even alkylphenol polyglycol ethers, but for many plant diseases they are little or no ineffective, which is related to their structure, lacquer and unsuitable combinations of pesticides or potential pests. Icítlov. The present invention successfully solves these problems.

SUMMARY OF THE INVENTION

The present invention is based on tat 1. The spray mixture ap11 is forged in the form of an aqueous solution, emulsion and / or dispersion consisting of 0.006 to 5% by weight. thymol and / or carvacrol in native form and / or z. at least a portion thereof of water-permeable salts of 0.000002 to 0.002% by weight. of at least one of the three phenyl tin rope dyes selected from fucsin, pyrocateches of new vlolet.1, crystal voletol, rhodainin D, t.ymol su 1 foft.and 1 eine, methyl green, had achlt green brilliant green and their zinc salts From 0.00006 to 0.5% by weight. and / or 0.00005 to 5 wt.%. copper salt.

Fung i t at. The spray mixture can also be prepared such that the water-soluble salts of thymol or carvacrol are their salts, most preferably their sodium, potassium and ammonium salts.

The fungal 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 antenna surfactant comprises at least one or more sodium or calcium alkyl benzene sulphonate, the alkali salts of the higher fatty acids C 1, C 2 O partial esters of at least partially neutralized organoesters of trihydrogenphosphoric alkali metal hydroxide or triethanolamine.

No ion tenzld is selected from products polyadícle ethylene oxide to fatty alcohols having the number of carbons 10 to 21 or alkyl phenol y _of the alkyl on the number of carbons from 8 to 18, the products polyadícle ethylene oxide to fatty amine, or carboxylic acid, the alkyl of the number of carbon 8 to 22, polyadenethylene oxide products for alkanolamines and additions or triphenylmethane growth rates. imulated mixtures l.

a mixture of 1 carvacro1 derivatives of the condensation of alkanolamines with higher carboxylic acids.

In the preparation worked. The sprayed mixture may also be prepared in such a way that any of the above-mentioned components can be prepared both separately and together, the resulting effect not being dependent on the order of addition of the individual components but on their final concentration. Advantageously, the above-mentioned constituents 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 dyes as the most effective fungicidal and antioxidant components.

The most effective fungal components in the sprayer are thymol (3-hydroxy-4-isopropyltoluone) and its isomer (2-hydroxy-4-isopropyltoluene), belonging to the phenol family, which are still used as antiseptics in human medicine. Three phenyimethane dyes, which are components of the spray mixture, from the point of view of their biological activity can be classified into the group of disinfectants, antiseptics, antimycotics and anemia of linentics, some of which have kept their practical importance in human medicine for more than a century as diagnostic dyes, in the coloring of pharmaceutical preparations, in the treatment of inflammation and mycoses, or in the parasite deprivation of the gastrointestinal tract, utilizing their anthropolytic properties compared to the lower animal forms. The widespread use of the various properties of this class of compounds in other areas, such as cosmetics and food, ensures the toxic safety of these components of the spray composition. In view of these facts, despite the different concentrations of t.r and Tony 1 methane dyes, which in the spray mixture must be several rows lower than in the above-mentioned application areas, their fungicidal effects would be expected. However, experimental results indicate that the use of ΓυΛsine (Basic Fuchsln), pyrocathohrionic fleets (gentlanic fluffy), pyrocatechin sh 1 fof t.aline /, crystal prills (Basic vlolet 3, methrosaniline), rhodamine B / Basic Violet. 10, tetramethylrodamine (thymolsulfophthaloin), methyl green (Basic Blue 20), malachite (Basic Green 4), brilliant green and its zinc salt (Basic Green 1) as components of the fungal state of the mixture as growth promoters , because they support;, c. the leads-.DIV.

I.

photosynthesis. Their properties as preservatives against fruit overgrowth (against the rotting of tomatoes and cucumbers) as well as their anthelmentic properties can also be applied. However, the use in the form of photosynthesis stimulators is very sensitive to the concentration. The optimum concentration in the spray mixture is manifested by a deepening of the green color of the leaves of the treated cultures over a period of up to 30 minutes, which color is resistant to water washability (rain). This suggests that some components react with the culture being treated. The pronounced insecticidal effects of the three phenylmethane dyes to the lower species of sucking insects are manifested at such concentrations in the test zines, which still provide an upper, yet acceptable limit of their use as growth promoters. Therefore, the insecticidal properties of the three phenylmethane dyes in the coating composition should be evaluated only as marginal. The use of these substances at the optimum concentration results in an accelerated recovery of the newly grown offshoots on the treated culture, usually even when the lower growing time is already largely attacked. Further, it is preferred that the three ny nyimethane dyes themselves are not toxic, but that they may be used as growth promoters at extremely low concentrations.

A further group of substances in the spray mixture are surfactants which modify the surface drinkable between the spray mixture and the tissue of the chemically treated culture. But with some surfactants such as e.g. alkylphenols, at. Their increased biological activity may be adversely affected, since far more effective fungicidal components are present in the spray mixture, such as possibly some of the upper-tonic surfactants could be present ^: ^ - ^c It is sufficient to use lower concentrations thereof .

Described work with tat. The latter composition, which, like other types of pesticides, may have an even wider spectrum of effects. It may also have been modified with other types of spray mixtures that have been tried for a long time, and in particular a combination with copper soles is particularly suitable, where not only their synergistic effect, but also the combined effect can be observed.

The most effective lunglstatic components in the sprayed mixture are thymol (3-hydroxy-4-isopropyltoluene) and its isomer carvacrol (2-hydroxy-4-isopropyltoluene) belonging to the group of phenol derivatives whose antimycoseptic properties in the field of human

S) with them to create new types of compounds, medicine has long been known, but they are poorly water-soluble in their native form. When copper ions are present in the solution, their copper salts react and form their copper salts, which are characterized by higher biological activity and dissolution as the original mixture of the components in the sprayed mixture. This is prJ. in practical application, it shows an increased effect of the sprayed mixture, i.e. as a synergistic effect. Temperature can be used to accelerate the equilibrium reactions. If triphenylmethane dyes are present in the reaction system, the copper salts of the three phenylmethane dyes will also be formed as effective fungal, growth, and antholmentic blend components; 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 the copper salts, which may be 100 to 500 times lower than that of industrially used copper preparations.

An advantage of the fungicidal spray composition according to the invention is that it has a high fungicidal effect even when applied to the crops already affected, in particular cucumbers, grapevines, tomatoes, apricots, peaches and the like. practically with others, long-term concentration of vegetation treatment and non-toxic coke tours of the components and the possibility of modification by the tested preparations is very resistant to rain wash, as well as the possibility of long-term storage, its disinfectant, conservative, anthelmont as well as growth and mulation effects, as well as the relatively wide concentration range of the components in the spray mixture, but the multiple use of higher concentrations of components in the mixture usually does not result in damage to the cultures. V i. ΛΛ and last but not least ¹ \ ^ 'significant Synergistic effect of components fungistatic spray mixture.

The effects of the spray mixture and the manifestations of flCU in 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. For the chemical treatment of peach-like curls, the use of spraying is particularly advantageous since peaches in the growing season do not tolerate copper-based sprayings applied in the form of copper sulphate or copper oxycell or copper oxide to achieve an effect in sufficiently high concentrations. This relatively common disease usually results in thread ^ Just destroying the entire crop, but can lead to the whole tree drying up. The fungistatic composition described, especially when applied at the time of vegetation, causes the disease not to appear in the vegetation period, and can also be applied in the flowering period at the indicated concentration of solution Ju. Its symptoms depend on the degree of infestation of the treated tree. After the first spraying, the infested leaves, which are overgrown with fungi, fall off and the places 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 growing faster and larger, the latter of which, in the case of fallen leaves, result in an accelerated growth of new leaves, so that during the ripening period they provide normal parenting. 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 infested with fungal diseases, with the difference that its efficacy is lower and therefore it was appropriate to repeat 1 to 2 times within 5 to 10 days according to the condition treated growth In the case of spreading powdery mildew and chrysality, the apple tree and the liqueur, even for the complete eradication of the disease, sprayed _VJ fe ~. 2-3 times. Also, in the chemical treatment of grapevines against, various psoriasis diseases, peronospore, powdery mildew and the like, it is possible to observe a substantially more uniform development of berries, to prevent drying of bunches and the growth of new offshoots. It should be pointed out, however, that the vines require more regular treatment, at least four times chemical spraying during the growing season, and the bedding may be moved 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 apoploxal-infected apricots against which there is currently no sufficiently effective chemical agent which attacks especially young individuals and results in the death of whole trees, the effectiveness of the spraying depends on the presence and concentration of tr, phenylene dye . More effective are those formulations whose spray mixture has been 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 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 apoplexle 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 three phenylene dye to be a crystal or pyrocat. by spraying on not yet challenged Individuals or during a period of vegetation calm. Non-annual experiments with the chemical treatment of cucumbers against the cucumber peronospore, causing their substantially lower yields, have shown that the described sprayer 1 and the mixture appear to be one of the most effective means against this disease. In the case of chemical treatment of cucumbers, it is advisable to treat the cucumbers in the months of April to June, as well as cucumbers according to the condition of the crop, ie using approximately half of the individual components in the spray mixture at two three-week intervals. between sprayings and increased concentrations of the individual components in the sprayed mixture. Approximately until mid-August It is advisable to apply the spraying every week or in the three to ten minutes i nerval och. However, in the second half of August, which is also dependent on the weather, intervals between

With individual spraying he prolonged up to three weeks. The effects of the sprayed 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 war-growing cultures show the birth rate until the first frosts arrive, especially on newly grown offshoots. impacted. At the same time, the substantial retardation of over-examination and fruits shows the conservative properties of the spray. A similar situation, but on a smaller scale in terms of resistance, may be observed / w tomatoes. In the chemical treatment of peppers, which in addition to fungal diseases are often also infected with sucking insects, it is even possible to observe an increase in the birth rate.

A markedly positive, synergistic effect of the spray mixture even in the presence of 1 cupric ions was observed in the chemical treatment of onions, garlic, leeks, beans, carrots, parsley and potatoes.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

A sprayable mixture was prepared in the form of an aqueous dispersion consisting of 0.5% by weight. thymol in native form and 0.001% by weight. of a benzene sulphonate-based reagent.

Example 2

A sprayable mixture was prepared as an aqueous emulsion consisting of 0.5% by weight. carvakrnl in native form, and 0.01 wt%. m.p. a reagent prepared by polyaddition of ethylene oxide to tin oil.

Example 3

A sprayer was prepared and a mixture applicable in a water-soluble form consisting of 0.05% ammonium salt of thymol, 0.0008% limot, 1% brilliant green night salt, 0.01% by weight. tenzyl, prepared by polyaddition of ethylene oxide to castor oil.

Example 4

A booster was prepared and a mixture applicable in water-soluble form consisting of 0.001.5% by weight. ammonium salt of thymol, 0.001% lithium. % of a reagent prepared on the basis of partial organoesters of the acid chloride, 0.0007% by weight.

pyro-choline violet and 0.004% copper oxide.

Example 5

A spray and mixable and water-soluble form consisting of 0.003% by weight was prepared. ammonium salt of tyinolone, 0.004 wt%. % of a surfactant prepared on the basis of partial organoesters of t.i. and hydrogenphosphoric acid, 0.0015% by weight.

brilliant zeleng and 0.008 wt.% copper oxychloride.

à

Example 1 and 6

A sprayer 1 was prepared and the mixture aptable in water-soluble form consisting of 0.015 wt%. of ammonium salt of thymol, 0.01% by weight of t-amide prepared on the basis of partial organoesters of trihydrogenphosphoric acid, 0.002% by weight. pyrokaline quinquine. i and 0.04% by weight. copper sulphate.

Example 7

A sprayable composition applicable in a water-soluble form consisting of 0.3 wt. ammonium salt of thymol, 0.02 wt%. % of the tonside prepared by polyaddition of ethylene oxide to nonylphenol, 0.005% by weight. and 0.3% by weight.

copper oxyehlorldu.

Example 8

A sprayable mixture applicable in the form of an emulsion in water consisting of 0.000% hin was prepared. potassium thymol salt, 0.01 wt%. an emulsifier consisting of an equi-molar mixture of flodene 1, sodium phosphate 1 and ammonium lauryl sulphate, 0.0001% by weight. and 0.05 wt. oxyeh1 or 1du copper.

Example 9

The spraying mixture of Example 4 was used for preventive chemical treatment of vines, cucumbers, carrots, tomatoes, peppers, parsley, garlic and onions. Spraying was repeated every two to three weeks. Symptoms of powdery mildew occurred only in vines 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, the symptoms of pyospora appeared in cucumbers and powdery mildew attacked the grapevine. With another comparable blend as in Example 4, and by omitting cuprous oxyhloride, the symptoms of pergnospore also appeared on the cucumbers, and the powdery mildew clearly attacked the grapevine.

Example 10

Sprayers :! the mixture of Example 6 was used for the chemical treatment of grapevine, cucumber, rose, gooseberry, powdery mildew, peach-infected peach and apricot-infected apricot. In gooseberries and currants, the cfcv observed a substantial effect on the spread of the disease. On the other hand

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ľ »* * t f '. *, i' S '/ N ¹ p! In the case of the vine and cucumbers, the growth of new offshoots was observed, the peaches and roses were heavily attacked. the whole leaves withered and fell off while being / ιιΟίΐγτ. to observe the accelerated growth of new leaves. For apricots, the wilting of the leaves of the whole branches was observed to be stopped, but the spraying had to be applied in a series of weekly to monthly cycles throughout the growing season. However, by omitting brilliant green and increasing the concentration of copper oxychloride from 0.008 · / · mass. to 0.08% of the mass, the accelerated growth of the offshoots was not observed in cucumbers and, moreover, they remained partially attacked by perennial, as well as the curl of peaches subsided considerably more slowly. Challenged branches of apricots 11.

Example 11

The 1 and 1 fungal spray and blend of Example 5 were used to chemically treat the strains of apple, pear, cherry and plum infested with fungus during the vegetation period, with the brush applied. After a multiple spray application over 14 days, the JpI person was discarded. However, by omitting the surfactant and increasing the copper (N) chloride to 0.01 wt%. the effect did not appear until five times with a freshly prepared spray mixture. When applying the previously prepared mixtures and mixing them with an electric stirrer before use, the effect did not take effect until 8 weeks.

Example 12

The sprinkler 1a blend of Example 7 was used to chemically treat vines, apples, pears, plums, cherries, peaches, apricot apricots, currants and roses during the vegetation period (before spring break). Spraying was applied once. At the beginning of the vegetation period, the treated plants showed significantly less prevalence of fungal and fungal diseases, powdery mildew and apoptosis pH than untreated plants. By omitting copper oxychloride, the reduction in fungal disease was less noticeable.

Claims (4)

A fungicidal spray mixture, ap.1, obtainable in the form of an aqueous solution, an emulsion and / or an alobo dispersion, characterized in that it comprises 0.005 to 5% by weight. thymol and / or carvacrol in native form and / or 2 of their water-soluble salts; * 0.000002 to 0.002% of limes, at least one of the three lethane dyes selected from fucsin, pyrocatechin violet, crystal violet, rhodamine Π, thymolsulfophthalein, methyl green, had 1 LoveJ green, brilliant green, and their zinc salts, 2 0.00005 to 0.5% by weight of an antenna and / or non-ionic surfactant and 1 to 15% by weight of a copper salt. Fungistatic spray zines according to claim 1, characterized in that the water-soluble salt of thymol and / or carvacrole is an alkali salt, preferably a sodium salt and / or an ammonium salt. Fungistatic spray mixture according to claims 1 and 2, characterized in that the copper salt is copper oxychloride and / or copper sulphate. A fungicidal spray mixture according to claims 1 to 3, characterized in that the anionic surfactant forms at least one of the following: and / NTL · 'alkylbenzénsuIfónanu from among sodium or calcium, alkali salts of higher fatty acids and C _{jo 2 J} C, partial / Ca / ester least a portion of neutra1 izovanýeh organoesterov trIhydrogénfosrorečnej. alkali metal hyaline or triple anion / y. A fungicidal spray mixture according to claims 1 to 4, characterized in that the non-ionic surfactant is selected from polyaddition products of ethylene oxide to aliphatic alcohols having a carbon number of 10 to 21 and / or alkyliphenols _/ with an alkyl number of carbon numbers of 8 to 18, polyaddition products of ethylene oxide to higher aliphatic amines and / or carboxylic acids having an alkyl number of 8 to 22 carbons, polyaddition products of elylene oxide to alkanoamines and addition and / or condensation of alkanoamines with higher carboxylic acids.