Description
Glycerine as fungicide or bactericide active substance
Technical Field
The present invention relates to the use of glycerine and/or its derived compounds as an active fungicidal and bactericidal substance. The present invention also relates to a fungicidal and bacterial compound comprising glycerine and/or its derivatives as an active substance, in combination with at least one other active substance selected from the common fungicides and bactericides, as well as use of the compound in the preventive and/or curative treatment of plants .
Background Art
The presence on the market of a large number of substances and compounds used for controlling diseases caused by fungi and bacteria in agricultural crops, in particular in vine growing, vegetable growing and fruit growing is known.
Most fungicidal and bactericidal substances and compounds are of synthetic origin, for example dithiocarbamates . Such categories of substances have a systemic and/or contact effect on diseases caused by fungi and bacteria. Alternatively, there are substances and compounds with a fungicidal and bactericidal action of natural origin, such as sulphur and copper, the latter in the form of a sulphate or chloride .
One of the limits of the above-mentioned substances and compounds is the fact that in the doses tolerated by agricultural crops, the action against fungi and bacteria is sometimes limited. For this reason, operators in the sector are forced to use more concentrated doses of fungicidal and
bactericidal substances, relative to the limit of concentration tolerated by the plantations.
The use of increased concentrations results in phenomena by which the plant is poisoned. The use of substances containing copper, in the form of a sulphate, chloride or hydroxide, on fruit plants may cause the formation of typical brown - reddish spots on the outer surface of the fruit.
Moreover, the copper reduces the size of the fruit and, copper residues dispersed in the soil prevent the plant from absorbing nutritional elements such as iron.
In the case of grapevines, the use of substances containing copper has a negative effect on the quality of the bunch of grapes. Moreover, as is known, the collateral effect of fungicidal substances in general may be varying degrees of toxicity for humans, animals and the environment.
Other disadvantages, which impose the use of bactericidal and fungicidal substances in limited and controlled concentrations, are linked to problems deriving from their build-up in the soil.
Generally, an excessive build-up of said substances in the soil may lead to the risk of pollution of agricultural land.
Moreover, excessive use of said substances over time leads to an increase in the ability of bacteria and fungi to resist them. For this reason, fungicidal and bactericidal substances may become less effective over time and, therefore, new substances must be perfected.
Therefore, the need remains for fungicidal and bactericidal substances and/or compounds with limited toxicity, high efficiency at low concentrations for the preventive and curative treatment of diseases caused by fungi and bacteria on agricultural crops, in particular in wine growing, vegetable growing and fruit growing. In particular, biodegradable fungicidal and bactericidal substances and/or compounds are still needed, which are also
able to limit the problems linked to a build-up of polluting substances in the soil.
The use of glycerine or glycerol (1, 2, 3-propantriol) as an additive in formulas for agricultural use is known. Moreover, document IT 1195284 describes the use of glycerine as an additive for the preparation of water-based suspensions containing anti-parasitic substances to be distributed from the air. Glycerine solves the technical problem of preventing the drift effect. Document GB 2107987 describes the preparation of compounds containing glycerine as an additive, the quantity of the latter being between 5 and 95% by weight. Said compounds are added to water-based pesticide compound solutions, suspensions or emulsions containing between 3 and 30% pesticide by weight. Document EP 862861 describes acaricidal and insecticide compounds comprising at least one ester of a fatty acid selected from monooleate glycerine, monolinolate glycerine, monocaprylate glycerine and others .
Disclosure of the Invention
None of the documents in the background art illustrate or suggest the use of glycerine as it is, as an active substance, for combating fungi and bacteria. In particular, none of the documents in the background art illustrate or suggest the use of glycerine as it is, as a substance with fungicidal and bactericidal action in the preventive and curative treatment of diseases which develop in agricultural crops, in particular in wine growing, vegetable growing and fruit growing.
Moreover, no documents illustrate or suggest the use of glycerine as an active substance in combination with other active substances, the latter selected from known substances which have a fungicidal and bactericidal action, in the preventive and curative treatment of diseases which develop in agricultural crops and in fruit plantations . Moreover, no documents illustrate or suggest that, when combined with other active substances, glycerine allows a
reduction in the quantities and concentrations of the latter substances in the preventive and curative treatment of plants.
The technical problem which prompted the present invention was the need to overcome the limits and disadvantages apparent in the background art.
This problem was solved by the Applicant, who surprisingly found that glycerine as it is or in a water-based solution possesses unexpected fungicidal and bactericidal properties against some types of fungi and bacteria. In particular, glycerine as it is, or a water-based solution containing glycerine, is successfully used in the preventive and/or curative treatment of many diseases which affect and devastate agricultural crops, in particular in wine growing, vegetable growing and fruit growing. Moreover, the Applicant found that as an active substance glycerine demonstrates a greater fungicidal and bactericidal action when used in combination with other substances with a known fungicidal and/or bactericidal action.
Finally, the Applicant found that glycerine, as an active substance, when used in combination with other active substances, allows a reduction in the concentration of the latter with good results.
A first aim of the present invention is the use of glycerine as an active fungicidal and bactericidal substance. Another aim of the present invention is to provide a fungicidal and bactericidal compound containing glycerine, as an active substance, combined with at least one other known fungicidal and bactericidal active substance.
Another aim of the present invention is the use of said fungicidal and bactericidal compound for preventive and curative treatments in wine growing, vegetable growing and fruit growing.
Other preferred embodiments are described in the dependent claims herein.
Further technical characteristics and advantages of the invention are more clearly illustrated in the detailed description which follows.
Glycerine (glycerol; 1, 2, 3-propantriol (C3H803) has the physical state of a viscous liquid substance at room temperature and a density of 1.26 g/cm3 at 25°C.
Glycerine is commonly marketed with a degree of purity of between 80 and 99% by weight.
For the purposes of the present invention, the glycerine used as an active substance as it is or in a water-based solution has a purity (concentration) not below 80%.
Glycerine is a substance of biological origin, obtained by hydrolytic processes applied to natural oils and greases.
The chemical properties of glycerine may be found in chemical manuals.
However, the high degree of solubility of glycerine in many organic and inorganic polar solvents must be emphasised.
In particular, glycerine has a high level of solubility in water and, therefore, is a very hygroscopic substance. Glycerine has a good degree of biodegradability, expressed as aerobic degradation and anaerobic degradation. The BOD, COD and BOD/COD data appears in chemical manuals. Moreover, glycerine is not bioaccumulable.
Glycerine has an LD50 value of more than 20,000 mg/kg of body weight (value measured on rat by inhalation) .
The Applicant found that glycerine used in a water-based solution has a preventive and curative action against fungi and bacteria which infest many agricultural and fruit crops.
The action of glycerine is probably due to a multi-site effect and, therefore, to a direct action on the fungus and bacteria. When glycerine makes contact, for example, with the outer surface of a leaf or fruit, it modifies the osmotic pressure .
Glycerine is a hygroscopic substance and acts on the competitive mechanism for the availability of water. Basically, glycerine competes with the fungi and bacteria for what water
there is available. By a hygroscopic action, the glycerine extracts water from the bacteria and fungi, preventing the latter from proliferating.
Glycerine also acts indirectly by stimulating the plant's defences against infections caused by fungi and bacteria.
In a preferred embodiment of the present invention, glycerine may be used as an active substance in the concentrated, undiluted, pure product state, since equipment now exists which allows a liquid substance to be nebulised and turned into dust, distributing it over a vast area. The technical possibility of nebulising a substance on large areas allows the glycerine concentration to be dosed on units of area.
The action of the glycerine does not produce the same results for all fungal infections .
In another preferred embodiment of the present invention, in the case of Oidium, that is to say, a fungus with a waxy surface, the use of glycerine as an active substance in combination with at least one other active fungicidal and bactericidal substance produces improved results.
Moreover, glycerine stimulates the formation of chlorophyll in the leaf.
Glycerine has a softening and toning effect on the surface of the leaf, stimulating the formation of chlorophyll and unfolding of the leaf.
The different operating mechanism of the glycerine operates in synergy with the other active substances, increasing their effectiveness thanks to its adhesive and coating power.
Water-based solutions containing glycerine preferably have a glycerine concentration of at least 0.05% (that is to say, 100 litres of water and 0.05 litres of concentrated glycerine). A glycerine concentration of at least 0.10% is even more preferable .
However, advantageous results are also achieved with higher concentrations, for example between 1 and 20%, depending on the type of equipment used to distribute the solution.
Alternatively, as indicated above, if modern equipment is available, glycerine may be used advantageously in its pure, undiluted concentrated state.
Advantageously, glycerine or a compound containing glycerine may be used in the preventive and curative treatment of the following fungi: Plasmopora viticola and spp, Phytophtora infestans and spp, Venturia inequalis and spp, Oidium spp, Fusarium spp, Botrytis spp, Penicilium spp, Septoria spp, Rusts spp, Cercospora spp and Taphrinia spp Advantageously, glycerine or a compound containing glycerine may be used in the preventive and curative treatment of bacteria such as Erwinia and Erwinia spp
Advantageously, glycerine or a compound containing glycerine may be used in the preventive and curative treatment of the following crops: fruit crops such as apples, pears, peaches, apricots, prunes and citrus fruits; grapevines; industrial crops such as tomatoes, potatoes, beet, maize; market gardening crops such as lettuce, cucurbits, strawberries; cereals such as wheat, barley, rye, millet, rice; flower crops such as roses, chrysanthemums, geraniums.
The fungicidal and bactericidal compound which forms the subject matter of the present invention comprises a hydrophilic solvent, glycerine as the active substance in combination with at least one other active substance selected from the group consisting of: copper, for example in the form of copper sulphate, copper chloride, copper oxychloride and copper hydroxide; phosphorous acid, for example in the form of alkaline salt of phosphorous acid or sodium phosphite, potassium phosphite, calcium phosphite, aluminium ethyl phosphite; salicylic acid, for example in the form of salicylic acid salt; sulphur.
In another preferred embodiment of the present invention, glycerine is used as an active substance in combination with at least one other substance selected from the group consisting of: diacetine (glyceryl diacetate) , TEGDA (triethylene glycol
diacetate CAS: 111-21-7), acetin glyceryl monoacetate CAS 102- 76-1 C3H5(OH)2OOCCH3.
The solvent is selected from the group consisting of: water, short chain alcohol C1-C4 and a mixture consisting of water and an alcohol in variable proportions .
Advantageously, the solvent is water.
The compound described above, preferably, includes an adjuvant such as a surfactant selected from those commonly used in the sector. The compound is in liquid form with a density value which varies depending on the solvent, the surfactant used, the glycerine concentration and the type of fungicidal and bactericidal substance used.
The experimental part which follows, supported by examples 1 to 10, should not be considered as limiting the scope of the present invention. EXAMPLE 1
Type of plant: pear; nine-year old fruit-bearing plant; Conference variety. Disease: Al ternaria al terna ta .
Treatment: begun two weeks before flowering and terminated two weeks before the fruit was harvested; the treatment was repeated every eight days for a total of 20 treatments.
Application: a first test sample was treated with a solution consisting of (2 litres) of glycerine and (1000 litres) of water per hectare.
The solution was distributed using a sprayer with internal combustion engine.
A second test sample with the same characteristics was treated using the same methods with a solution containing the synthetic fungicide Thiram.
Thiram, CAS: 137-26-8; [ (CH3) 2NCH] 2S2, is an active ingredient with a fungicidal action.
A third test sample was not treated and was considered the control.
The results are shown in Table 1 and refer to the number of spots on 200 leaves and 100 pieces of fruit, found at the time of harvesting the fruit.
Table 1
The % effectiveness was calculated, for example in the case of leaves treated with the glycerine, as follows: 5 spots still present after treatment;
125 spots initially present in the sample consisting of 200 leaves; 125 - 5 = 120 spots were cured
120:125=X:100 X=120.100/125 X=96% effective.
Fruit (pear) trees treated with glycerine have softer leaves which are greener in colour than trees in the comparative test treated with the synthetic fungicide Thiram. The outer coating of the fruit, treated with glycerine in a water-based solution, shows a reduction in the number and size of the spots (rustiness) .
The fruit treated in this way has a better appearance and is preferred by the consumer. Moreover, the glycerine is less toxic than synthetic fungicides and is more biodegradable.
The economic aspect of the treatment is very important, since glycerine is a substance which is less expensive than fungicidal and bactericidal substances in general . EXAMPLE 2 Type of plant: apple; six-year old fruit-bearing plant; Granny Smith variety.
Disease: Venturia inequalis (Scab).
Treatment: begun three weeks before flowering and terminated two weeks before the fruit was harvested; the treatment was repeated every eight days for a total of 24 treatments.
Application: a first test sample was treated with a solution consisting of (2 litres) of glycerine and (1000 litres) of water per hectare.
The solution was distributed using a sprayer with internal combustion engine.
A second test sample with the same characteristics was treated using the same methods with a solution containing the synthetic fungicide Maconzeb.
A third test sample was not treated and was considered the control .
The results are shown in Table 2 and refer to the number of spots on 100 leaves and 100 pieces of fruit, found at the time of harvesting the fruit.
Fruit (apple) trees treated with glycerine have softer leaves which are greener in colour than trees in the comparative test treated with the synthetic fungicide Maconzeb.
The outer coating of the fruit, treated with glycerine in a water-based solution, shows a reduction in the number and size of the spots (rustiness) .
The sample treated with glycerine only showed a lower number of mites than the sample treated with Maconzeb only. EXAMPLE 3
Type of plant: grapevine; three-year old grapevine; Regina variety.
Disease: Plasmopara vi ticola .
Treatment: terminated three weeks before the bunch was harvested; the treatment was repeated every seven days for a total of 12 treatments.
Application: a first test sample was treated with a solution consisting of (1.5 litres) of glycerine and (800 litres) of water per hectare.
The solution was distributed using a sprayer with internal combustion engine.
A second test sample with the same characteristics was treated using the same methods with a solution of a fungicide in the form of water-dispersible granules with a copper hydroxide base.
A third test sample was not treated and was considered the control .
The results are shown in Table 3 and refer to the percentage of leaves infested and the percentage of bunches infested, found at the time of harvesting the bunches.
Table 3
The grapevines treated with glycerine have better developed leaves and bunches of grapes.
The above test reveals that an optimum result is achieved in the control of the Plasmopara vi ticola and Botrytis (fungus which causes the disease known as grey mould) with reference to the bunches treated and a good result against the proliferation of Oidium (fungus) . EXAMPLE 4
Type of plant: sugar beet; Beta vulgaris variety.
Disease: Cercospora beticola .
Treatment: begun upon verifying the presence of initial symptoms. Five treatments were carried out, at 14 day intervals .
Application: a first test sample was treated with a solution consisting of (3 litres) of glycerine and (600 litres) of water per hectare.
The solution was distributed using a sprayer with internal combustion engine.
A second test sample with the same characteristics was treated using the same methods with a solution containing copper sulphate.
A third test sample was not treated and was considered the control.
The results show that in the case of plants treated with glycerine, the disease control value was 85%, whilst in the case of plants treated with the copper sulphate, the disease control was 80% relative to the control.
Table 4
EXAMPLE 5
Type of plant: cereals such as wheat; Victo variety.
Fungus diseases: Puccinia , Fusarium, Septoria .
Treatment: begun at the end of tillering. 4 treatments were carried out, at 15 day intervals.
Application: a first test sample was treated with a solution consisting of (3 litres) of glycerine and (600 litres) of water per hectare.
The solution was distributed using a sprayer with internal combustion engine.
A second test sample with the same characteristics was treated using the same methods with a solution containing Maconzeb.
A third test sample was not treated and was considered the control.
The results of the test described above indicate that similar results were achieved using both glycerine and Maconzeb.
However, it must be highlighted that the glycerine has the advantage of being less toxic for humans and plants, and is more biodegradable than synthetic fungicides .
Table 5
Measured at milk ripening stage
The % leaf surface affected is evaluated by taking a sample of 100 leaves and, for each leaf, using a method known to experts in the sector to define a mean value of the area affected by the diseases.
In other tests, solutions containing a glycerine concentration of between 0.10 litres and 0.60 litres per 100 litres of water were used.
The treatments were carried out on some types of plants and against the diseases indicated below: plant grown disease
- strawberry Botrytis - rose Black spot and Oidium
- potato Phytophtora
~ ornamentals Puccinia and Cercospora
- vegetables Peronospora
These tests did not reveal any toxicity towards the plants treated. Good effects were also achieved against fungal infections caused by: Al ternaria , Venturia , Peronospora , Plasmopara, Cernospora and Botrytis .
Advantageously, treatment with solutions containing glycerine and water produced good effects against the bacterial disease caused by Erwinia amilovora .
Advantageously, glycerine can be used in preventive treatments before the onset of the disease or, alternatively, in curative treatments, that is to say, during the period in which the disease caused by fungi and bacteria has already developed.
The fungicidal and bactericidal properties of glycerine can be enhanced when glycerine, as an active substance, is used in combination with at least one other active substance selected from the active ingredients known as fungicides and bactericides.
Advantageously, in a preferred embodiment of the present invention glycerine is used in combination with at least one other active substance selected from the group comprising: copper, for example in the form of a salt of copper sulphate, a salt of copper chloride, copper oxychloride, copper hydroxide; phosphorous acid, for example in the form of alkaline salt of phosphorous acid or sodium phosphite, potassium phosphite, calcium phosphite, aluminium ethyl phosphite; salicylic acid, for example in the form of salicylic acid salt; sulphur. In another preferred embodiment of the present invention, glycerine as an active substance is used in combination with at least one other substance selected from the group comprising: diacetine (glyceryl diacetate) , TEGDA (triethylene glycol diacetate CAS: 111-21-7), acetin glyceryl monoacetate CAS 102- 76-1 C3H5(OH)2OOCCH3. EXAMPLE 6
Type of plant: soft wheat crop; Serio variety. Fungal disease: Puccinia , Fusarium, Septoria , Oidium . Treatment: a first treatment was carried out in the plant shooting period. A second treatment was carried out during the flag leaf period, with a third treatment at the start of the milk ripening period.
Application: a first test sample was treated with a solution consisting of (quantity used is indicated in Table 6) of glycerine and (600 litres) of water per hectare.
The solution was distributed using a shoulder pump.
A second test sample with the same characteristics was treated using the same methods with a solution of glycerine with copper hydroxide (quantities used are indicated in Table 6) and (600 litres) of water per hectare.
A third test sample with the same characteristics was treated using the same methods with a solution of glycerine with micronised sulphur (quantities used are indicated in Table 6) and (600 litres) of water per hectare.
A fourth test sample was not treated and was considered the control .
The results are shown in Table 6 and refer to the % control of the disease on the leaf and ear.
The test described above indicates that: a) the glycerine + copper hydroxide combination is more effective than glycerine used on its own, in the treatment of yellow rust and Septoria; and
b) the glycerine + micronised sulphur combination was more effective than glycerine used on its own, in the treatment of Oidium.
The % effectiveness was calculated based on the infestation on the control lot with value 100. EXAMPLE 7
Type of plant: grapevine; Schiava variety.
Disease: Peronospora (Plasmopora viticola) .
Treatment: begun during the post-flowering period. The treatment was carried out 4 times at two week intervals.
Application: a first test sample was treated with a solution consisting of glycerine (quantity used is indicated in table) and (700 litres) of water per hectare.
The solution was distributed using a shoulder pump. A second test sample with the same characteristics was treated using the same methods with a solution of glycerine with aluminium ethyl phosphite (quantities used are indicated in table) and (700 litres) of water per hectare.
A third test sample with the same characteristics was treated using the same methods with a solution of glycerine with salicylic acid (quantities used are indicated in table) and (700 litres) of water per hectare.
A fourth test sample with the same characteristics was treated using the same methods with a solution of glycerine with copper sulphate (quantities used are indicated in table) and (700 litres) of water per hectare.
A fifth test sample with the same characteristics was treated using the same methods with a solution consisting of a mixture of (aluminium ethyl phosphite and copper oxychloride) in (700 litres) of water per hectare
A sixth test sample was not treated and was considered the control.
The results are shown in Table 7 and refer to control of the Peronospora disease on the leaf and the bunch of grapes .
Table 7
The test described above indicates that: a) the sample treated with the solution containing glycerine showed optimum results, in terms of effectiveness against Peronospora on the bunch of grapes; b) the sample treated with the solution containing glycerine showed a less satisfactory result in terms of effectiveness against Peronospora on the leaf.
This result is due to the rapid growth of the leaves, which grow faster than the fruit.
The problem may be overcome using glycerine in combination with ethyl phosphite, salicylic acid and copper sulphate.
The results achieved indicate that some diseases encountered in vine growing may be countered biologically without the use of massive doses of substances containing copper and sulphur. EXAMPLE 8 The experiment was carried out at S. Michele all'Adige, on Cabernet Sauvignon grapevines and included two sets of comparative tests: control and treatment with a compound containing glycerine-based micro-elements used as a leaf fertiliser, the product being called MEDA F2. The tests were repeated three times. The product was applied 3 times, starting from the post-flowering period, at fortnightly day intervals and in doses of 300 cc/hl.
At two points in the vegetative season (pre-darkening and pre-harvesting) , the degree of attack by various diseases was observed on both the leaves and the bunches of grapes. On one hundred leaves and one hundred bunches of grapes for each test and for each repetition, the incidence of damage was evaluated, according to attack classes.
During the darkening period, samples of leaves were taken for analysis of the mineral elements from each lot.
At the time of harvesting, the production parameters (number of buds, number of bunches of grapes and production weight per plant) were measured for three homogenous plants considered representative of each lot and samples were taken in order to determine the qualitative composition of the musts.
As can be seen in the table relative to the data at the time of harvesting, the production parameters (number of buds, number of bunches of grapes and production weight per plant) were measured for three homogenous plants considered representative of each lot and samples were taken in order to determine the qualitative composition of the musts.
Moreover, as can be seen, the compound of micro-elements and glycerine used allows increased absorption of the microelements on the leaf due to the presence of the glycerine.
EXAMPLE 9
Type of plant: rose; rambling rose; Bianca variety.
Disease: Oidium .
Treatment: started when the presence of Oidium was verified, with the treatment repeated at two week intervals, soaking the plants to the dripping point.
Application: a first test sample was treated with a solutions of glycerine (quantity used is indicated in Table 9) .
The solution was distributed using a shoulder pump.
A second test sample with the same characteristics was treated using the same methods with a solution of glycerine combined with micronised sulphur (quantities used are indicated in Table 9) .
A third test sample with the same characteristics was treated using the same methods with a solution of glycerine combined with salicylic acid (quantities used are indicated in Table 9) .
A fourth test sample with the same characteristics was treated using the same methods with a solution of micronised sulphur only (quantity used is indicated in Table 9) . A fifth test sample was not treated and was considered the control.
The results are indicated in Table 9 and refer to the control of Oidium. The results were measured three weeks after the fourth treatment. Table 9
The test described above indicates that:
a) the sample treated with the solution containing glycerine combined with micronised sulphur showed optimum results, in terms of effectiveness against Oidium; b) the sample treated with the solution containing glycerine combined with salicylic acid showed good results, in terms of effectiveness against Oidium.
The results achieved indicate that the use of mixtures containing glycerine allow a reduction in the amount of sulphur used. EXAMPLE 10 (Seed dressing)
This test is for the dressing of wheat seeds against the disease caused by the fungus which affects the seeds.
The treatment was applied using laboratory and field apparatus .
The test was carried out both on Petri dishes in a germinator and on seeds sown directly in the field, using various varieties of wheat.
Table 10
Effectiveness is measured by counting the number of plants which emerged from 50 seeds placed in the soil, using the same number of seeds for each test.
Application of the glycerine for seed dressing provides a fairly good control of the fungal diseases both in Petri dishes and in the field.
The product could be validly applied in biological production, where there are no existing valid products for the protection of plants from fungal infections.