KR20150096544A - Pesticide composition comprising organic acid - Google Patents

Abstract

The present invention relates to an herbicide composition including organic acid, which effectively and safely promotes growth of crops and has an excellent effect of controlling paraquat-resistant weeds. The herbicide composition: does not cause resistance, which causes problems when an existing pesticide, particularly a paraquat peciticide, used to control weeds, is applied; can excellently promote growth of crops; and thus enables a user to safely and effectively cultivate crops.

Description

Pesticide composition comprising organic acid < RTI ID = 0.0 >

The present invention relates to a herbicidal composition, and more particularly to a herbicidal composition comprising an organic acid exhibiting excellent control effects against paraquat resistant weeds while promoting effective and safe growth of crops.

Of the herbicides developed so far, paraquat has the fastest expression rate. It is also an important agricultural material for the control of weeds in cropland and non-cropland with a broad weed spectrum.

However, herbicides with the same mechanism of action continue to be used in the same package each year, resulting in the emergence of resistant herbicide resistant weed species. It has been reported that 393 kinds of herbicide resistant weeds have emerged in the world. Among them, 28 species were reported to be resistant to paraquat, 1) resistance to metabolism of paraquat molecules, 2) limited penetration through cuticles, 3) ability to defend active oxygen produced by paraquat, 4 ), 5) paracetal intracellular isolation mechanisms, but some species have more than one resistance mechanism interrelated, while others can be explained by only one hypothesis.

The paraquat resistant 28 larvae were caused by continued use of paraquat, and some species have shown resistance in the past without exposure at all. Resistance to paraquat may be different in plant species or even in the same species. In the United States, differences in tolerance to paraquat were reported among the varieties actually used. In addition, the tolerance to paraquat varies according to the leaves in the same crop variety. Ohe et al. (2005) reported that the mature leaves from barley were more resistant to paraquat than the younger ones. Casano et al. (1994) The difference is due to the ability of the antioxidant enzymes to scavenge active oxygen and antioxidants. Such a mature leaf is more resistant to paraquat and environmental stress than a young leaf is a phenomenon that may occur in plants in general.

However, Kuk et al. (2006) report that the tolerance of cucumber to paraquat is greater in young leaves than in the same individual. In other words, the degree of tolerance of the leaves of four cucumber leaves when treated with paraquat was in the order of 4 leaf (young leaf)> 3 leaf> 2 leaf> 1 leaf. Especially, No signs of damage were seen. The difference in tolerance among these leaflets is related to the increase of antioxidant enzyme activity. According to various previous studies, the amber leaf extract has a paracootactivation effect and the substance that alleviates the activity of paraquat is presumed to be malic acid.

Accordingly, the present inventors have made efforts to develop a safe environmentally friendly pesticide having the effect of controlling the propagation of crops while promoting the growth of crops. As a result, it has been confirmed that when organic acids other than malic acid is treated, the growth of crops and the effect of controlling weeds are exhibited Thus completing the present invention.

One object of the present invention is to provide a paraquat herbicide comprising an organic acid which promotes the growth of crops and has an excellent control effect on paraquat resistant weeds.

Another object of the present invention is to provide a method for controlling weeds using the herbicide.

The present invention relates to a herbicidal composition comprising at least one organic acid selected from the group consisting of malic acid, oxalic acid, citric acid and tartaric acid.

The organic acids used in the present invention are tobacco ( Nicotiana tabacum L.), pumpkin (Cucurbita), cucumber (Cucumis sativus ), barley ( Hordeum isolated, purified or chemically synthesized from plant leaves such as Lactobacillus vulgare L.).

When the organic acid of the present invention is extracted from a plant, it can be extracted using an extraction solvent. The extraction solvent may be water, an anhydrous or a lower alcohol having 1 to 4 carbon atoms (methanol, ethanol, propanol, butanol) Acetone, chloroform, and 1,3-butylene glycol, alone or in combination of two or more, is preferably used, but not always limited thereto.

In addition, the organic acid can be obtained by a conventional purification process in addition to the extraction method using the extraction solvent. For example, by separation using an ultrafiltration membrane having a constant molecular weight cut-off value, separation by various chromatographies (made for separation by size, charge, hydrophobicity or affinity), and the like, Organic acids can also be obtained through fractionation.

The weeds which can be controlled by using the composition of the present invention include all-annual weeds or perennial weeds that occur in fields, fields, and non-agricultural lands, preferably one species selected from the group consisting of mung bean, Or more paraquat resistant weeds. Furthermore, the composition of the present invention shows the effect of promoting the growth of crops, including, but not limited to, maize, potatoes, and the like.

The herbicidal composition containing the organic acid according to the present invention may be diluted at a suitable dilution ratio using a carrier or the like which is conventionally used so as to be sprayable on weeds. In a specific embodiment, the herbicidal composition of the present invention may be diluted so as to be contained in an amount of 0.1 to 5% by weight based on the total weight of the composition. If the content of the herbicidal composition of the present invention is less than the above range, the desired weed control effect can not be obtained. If the content is larger than the above range, the effect of increasing the amount of the herbicidal composition is insignificant.

The composition according to the present invention can be prepared as a raw material or a low-concentration concentrate, and the end user can mix the diluted liquid as described above and dilute the liquid at an appropriate dilution ratio as needed to use the diluted preparation. Further, the composition of the present invention may be made to have a desirable dilution ratio. The compositions according to the present invention can be used in a wide variety of formulations such as flowable compositions, suspensions, microsuspension, suspension emulsions, wettable powders, granular concentrates, microemulsions, etc., .

The herbicidal compositions according to the present invention can contain one or more commonly used surfactants and other inert ingredients in general such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, preservatives, stabilizers, defoamers, , A sequestering agent, a dye, a pigment, a colorant and a polymer together with a solid and / or liquid carrier (for example, water). In addition, the composition of the present invention may further comprise a carrier of natural or synthetic, organic, or inorganic material which, in combination with the active substance, facilitates dispersal or application of the plant, seed or soil.

Since the herbicidal composition according to the present invention promotes the production of crops and is excellent in controlling the herbicidal effect of the herbicides, it can be separated from plants, and the side effects on the drawing are very low compared to the synthetic herbicides. Therefore, Is an eco-friendly formulation that does not cause environmental pollution or disturbance of ecosystem due to overuse of the environment and is very useful for the production of organic agricultural products.

The herbicidal composition of the present invention does not cause resistance which is problematic in the application of herbicides, especially paraquat herbicides, which have been used for conventional weed control, and can promote the growth of crops remarkably, .

FIG. 1 shows the results when corn was mixed with malic acid, oxalic acid, citric acid, tartaric acid, succinic acid or malonic acid mixed with paraquat The results are as follows.
FIG. 2 shows the results when corn was mixed with malic acid, oxalic acid, citric acid, tartaric acid, succinic acid or malonic acid mixed with paraquat The relative moisture content of corn leaves was measured.
FIG. 3 shows the results when corn was treated with malic acid, oxalic acid, citric acid, tartaric acid, succinic acid or malonic acid mixed with paraquat It is the result of measuring the excess oxide content of corn leaf.
Figure 4 shows that when corn was treated with malic acid, oxalic acid, citric acid, tartaric acid, succinic acid or malonic acid mixed with paraquat, And the content of hydrogen peroxide in corn leaves.
Figure 5 shows that when corn was treated with malic acid, oxalic acid, citric acid, tartaric acid, succinic acid or malonic acid mixed with paraquat, And the content of nitrogen peroxide in corn leaves.
FIG. 6 shows the results when corn was treated with malic acid, oxalic acid, citric acid, tartaric acid, succinic acid or malonic acid mixed with paraquat The chlorophyll contents of corn leaves were measured.
FIG. 7 shows the results of measurement of organic acid content of leaves of central zucchini leaves and organic acid content of leaves of central zucchini leaves treated with 100 μM of paraquat.
8 is a graph showing the results of measurement of organic acid content of leaves of squash leaves of zucchini leaves and organic acid content of leaves of central zucchini leaves treated with 100 μM of paraquat.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention, and it is to be understood by those skilled in the art that the present invention is not limited thereto It will be obvious.

Example  1: Organic acid ( organic acid ) Treatment In the paraquat  Determination of the leaf damage rate and relative moisture content of susceptible corn

1-1. Corn preparation with various organic acids

The seeds were sown in a round pot (7 × 7 cm) filled with horticultural soil, and the day / night temperature was 30 ± 2/20 ± 3 ℃. The light period was 14/10 hour / The relative humidity was 70%, and the light amount was 500 mu mol / m ² / sec for 10 days. Then, 100 μM of paraquat was added to the above-mentioned corn in the presence of malic acid, oxalic acid, citric acid, tartaric acid, succinic acid or malonic acid, And treated with 0.1%, 0.3%, 0.5% and 1% of the organic acid and 1% of the organic acid without paraquat.

1-2. Determination of paraquat susceptibility to corn leaf damage by organic acid treatment

In Example 1-1, herbicides prepared by mixing paraquat and organic acid in corn were treated at different concentrations and then grown for 24 hours to measure leaf damage rate with organic acids.

On the other hand, to investigate whether malic acid, oxalic acid and citric acid showing strong resistance to paraquat damage even at lower concentration than the basic concentration, it was mixed with paraquat and treated with corn at a concentration of 0.01 and 0.05%. As a control group, corn without treatment with paraquat herbicide and organic acid was used. The results are shown in Fig.

As a result, the damage rate of leaves of maize treated with paraquat mixed with malic acid, oxalic acid, citric acid and tartaric acid was decreased with increasing concentration. On the other hand, corn treated with paraquat treated with 0.1% or more succinic acid had a similar damage rate to corn with paraquat alone, whereas corn treated with paraquat with 1% malonic acid had a leaf damage rate of about 50% It looked.

On the other hand, maize treated with low-concentration 0.01% of malic acid mixed with paraquat showed 80% leaf damage rate. When oxalic acid was mixed with paraquat and treated at low concentration, it was damaged only at 0.01% concentration. No damage was seen. When citric acid was mixed with paraquat and treated at low concentration, it showed about 50% and 30% damage at concentrations of 0.01% and 0.05%, respectively.

1-3. Measurement of relative moisture content of corn susceptible to paraquat by organic acid treatment

In Example 1-1, the herbicide mixed with paraquat and organic acid in corn was treated for each concentration, and the relative moisture content of corn was measured according to organic acid while growing for 24 hours. As a control group, corn without treatment with paraquat herbicide and organic acid was used.

 Relative moisture content (RWC) was assessed by gravimetric measurement. The fresh weight (FW) was measured immediately after excision of the upper part of the ground, and in a dryer maintained at 110 ° C for 48 hours And then weighed. The results are shown in Fig.

Experimental results showed that the water content of maize treated with paraquat mixed with organic acid was higher than that of corn without any leaf damage and healthy. Specifically, the moisture content of corn was similar to that of leaf, and malic acid, oxalic acid, citric acid and tartaric acid contained relatively large amounts of moisture in the leaves, but relatively low contents of succinic acid and malonic acid were found. On the other hand, malonic acid shows low water content even when only 1% of malonic acid is treated alone.

Example  2: Organic acid ( organic acid ) Treatment In the paraquat  Excess oxides of susceptible maize ( superoxide , O ₂ ^- ) Content measurement

In Example 1-1, the herbicide mixed with paraquat and organic acid in corn was treated for each concentration, and the leaves of the corn that had been grown for 24 hours were harvested and frozen in a freezer at -80 ° C. The excess oxide content was measured by hydroxylamine oxidation using the spectrophotometer method described by Wang and Luo (1990). As a control group, corn without treatment with paraquat herbicide and organic acid was used. The results are shown in Fig.

As a result, the content of excess oxides of corn mixed with succinic acid and malonic acid in paraquat was higher than that of corn mixed with malic acid, oxalic acid, citric acid and tartaric acid.

Example  3: Organic acid ( organic acid ) Treatment In the paraquat  Hydrogen peroxide in susceptible corn ( hydrogen Peroxide , H ₂ O ₂ ) Content measurement

In Example 1-1, the herbicide mixed with paraquat and organic acid in corn was treated for each concentration, and the leaves of the corn that had been grown for 24 hours were harvested and frozen in a freezer at -80 ° C. Then, 0.1 g of the corn leaf was placed in a mortar, and 3 ml of a 50 mM phosphate buffer (pH 6.8) solution was added thereto, followed by centrifugation at a temperature of 4 ° C at a rate of 6,000 × g for 25 minutes. Next, 1 ml of 0.1% titanium chloride and 20% H ₂ SO ₄ solution were added to the centrifuged supernatant, followed by centrifugation at a temperature of 4 ° C for 15 minutes at a rate of 6,000 × g. The absorbance of the supernatant was measured at a wavelength of 410 nm using a spectrophotometer to measure the hydrogen peroxide content. As a control group, corn without treatment with paraquat herbicide and organic acid was used. The results are shown in Fig.

As a result, the hydrogen peroxide content in the maize treated with succinic acid and malonic acid was found to be similar to that in the corn mixed with paraquat, and the amount of hydrogen peroxide was measured as compared with the maize treated with only 1% .

Example  4: Organic acid ( organic acid ) Treatment In the paraquat  Lipid peroxides of susceptible corn ( malondialdehyde , MDA ) Content measurement

In Example 1-1, the herbicide mixed with paraquat and organic acid in corn was treated for each concentration, and the leaves of the corn that had been grown for 24 hours were harvested and frozen in a freezer at -80 ° C. Then, the corn leaf was placed in a mortar and 5 ml of a solution containing 0.5% 2-thiobarbituric acid (TBA) dissolved in 20% ferric thiocyanate (TCA) was ground and polished and centrifuged at 20,000 × g for 15 minutes The supernatant was taken. Then, the supernatant was heated at 100 ° C for 25 minutes, cooled in an ice box, and then centrifuged at 20,000 × g for 15 minutes. The supernatant thus obtained was analyzed by an absorption spectrophotometer at 532 nm Absorbance was measured and corrected to the absorbance value at 600 nm. The culture broth was mixed with a solution of 0.5% 2-thiobarbituric acid (TBA) in 20% ferric thiocyanate (TCA) at a ratio of 1: 1 (v / v) and the absorbance was measured . The MDA content was calculated using a molar extinction coefficient of 156 mM ^-1 cm ^-1 . The calculated MDA concentration of the cultured leaf and the leaf was expressed as the total MDA content in terms of biomass weight / sugar. As a control group, corn without treatment with paraquat herbicide and organic acid was used. The results are shown in Fig.

As a result, the MDA content of corn treated with succinic acid and paraquat was higher than that of corn mixed with other organic acids.

Example  5: Organic acid ( organic acid ) Treatment In the paraquat  Chlorophyll of susceptible maize ( Chlorophy Ⅱ) Content measurement

In Example 1-1, the herbicide mixed with paraquat and organic acid in corn was treated for each concentration, and the leaves of the corn that had been grown for 24 hours were harvested and frozen in a freezer at -80 ° C. Then, 0.1 g of the frozen leaf was placed in a mortar, and 5 ml of dimethyl sulfoxide (DMSO) was added thereto. The chlorophyll was extracted for 48 hours under dark condition. The absorbance was measured at 645 nm and 663 nm using a spectrophotometer. 1 was used to calculate the chlorophyll content. As a control group, corn without treatment with paraquat herbicide and organic acid was used. The results are shown in Fig.

[Experimental Equation 1]

Chlorophyll II (mg / L) = [(20.2 x A ₆₄₅ ) + (8.02 x A ₆₆₃ )] x dilution value

As a result of the experiment, the content of chlorophyll in corn treated with malic acid, oxalic acid and tartaric acid by mixing paraquat was measured, but corn treated with succinic acid and malonic acid mixed with paraquat showed low chlorophyll content.

On the other hand, when treated with only organic acid, the corn leaf treated with only 1% of malonic acid showed low chlorophyll content.

Example  6: of the amber Leaf classification  Organic acid content measurement

Central zoos (joongangaehobak) were purchased from the central nursery and purchased from the modern nursery (wonhiaehobak). Then, the grown zucchini were treated with 100 [mu] M paraquat alone. Thereafter, 20 ml of distilled water was added to one or four leaves of the above-mentioned leaves of the zucchini leaf, and the mixture was ground with a homogenizer (homogenizer AM-11, Nissei Corp., Japan). The extract was filtered with a whatman 2 filter paper, After washing twice with water-saturated ether, the aqueous layer was concentrated under reduced pressure and diluted with 20 ml of distilled water for HPLC. A portion of it was passed through a C18 cartidge and the filtrate was filtered through a 0.45 μm membrane filter. The HPLC conditions are shown in Table 1 below. As a control group, zucchini without paraquat herbicide treatment was used. The results are shown in Fig. 7 and Fig.

Tartaric acid, malonic acid, lactic acid, cetic acid, citric acid and malic acid were detected in the central and middle noodles, and the contents of citric acid and malic acid were higher in the four leaves than the one leaf.

In particular, the content of citrate and malic acid in central courgette was higher than that of one leaf in four leaves. On the other hand, when treated with paraquat, the content of citric acid was similar to that of the control group, but the content of malonic acid in the four leaves was reduced by about 3 times (FIG. 7).

The content of citric acid and malic acid was higher than that of the control (Fig. 8), whereas the content of citric acid and malic acid was higher than that of the control.

Claims (4)

A herbicidal composition comprising at least one organic acid selected from the group consisting of malic acid, oxalic acid, citric acid, and tartaric acid.
[3] The herbicidal composition according to claim 1, wherein the herbicidal composition comprises the organic acid in an amount of 0.1 to 5% by weight based on the total weight of the composition.
The herbicidal composition according to claim 1, wherein the herbicidal composition is selected from the group consisting of a surfactant, a protective colloid, an adhesive, a thickener, a thixotropic agent, a penetrant, a preservative, a stabilizer, a defoamer, a cryoprotectant, a sequestering agent, a dye, Lt; RTI ID = 0.0 > a < / RTI > solid and / or liquid carrier.
A method for controlling weeds using the herbicidal composition according to claim 1.

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