KR101313261B1 - Copper compounds for crop and preparing method thereof - Google Patents

Abstract

The present invention relates to a high-functional crop copper and a method for producing the same, which has excellent antimicrobial activity, drug efficacy, efficiency, homogeneity, dispersibility, adhesion and shelf life, and has a wide range of application as compared to conventional copper. Crop for crops according to the invention is characterized in that it comprises a suspension of layered copper dihydroxide.

Description

Copper compounds for crop and preparing method

The present invention relates to a copper for crops and a method for manufacturing the same, and more particularly, by using a copper double hydroxide, which is a layered mineral, antimicrobial activity, efficacy, efficiency, homogeneity, dispersibility, adhesion and storage properties compared to conventional copper materials. The present invention relates to a highly functional crop copper and a method of producing the same, having a wide range of application of crops.

Unlike organic disinfectants in which drug resistance is generated, copper containing lime bordea liquid has been widely used as a protective disinfectant and has almost no resistance problems.

Copper, which is currently mainly used as an agricultural fungicide, includes a Bordeaux mixture, copper hydroxide copper sulfate, copper oxichloride and oxine copper.

However, the amorphous lime Bordeaux solution, which is most commonly used as a protective disinfectant among the existing copper, is less effective than a specialized drug for a particular disease, copper weakness occurs frequently, because it is difficult to manufacture a high concentrate There is a problem in that copper is accumulated in soil and crops due to high copper throughput per unit area. In addition, since the particle size is large, dispersibility and safety is low, the weakening of copper occurs during long-term storage, and the pH is more than 12.0 is difficult to be mixed with other drugs, the development of new copper is urgently required.

The present invention solves the problems of the conventional organic disinfectant and copper described above, having a high-functional crop protection function of high stability, sustainability, dispersibility, copper activity and adhesion to plant surface without drug resistance An object of the present invention is to provide a new type of copper and a method of manufacturing the same.

Copper for crops according to the present invention for achieving the above object is characterized in that it comprises a suspension of layered copper dihydroxide.

In addition, the method for producing a crop copper according to the present invention is characterized by producing a suspension of a layered copper dihydroxide by adding an alkaline solution to a copper salt solution and coprecipitation.

The copper for crops according to the present invention is composed of a suspension form of a copper dihydride, which is a crystalline mineral, and has excellent stability and storage property, and has an effect of reducing the weakness of copper compared to a conventional lime bordeaux solution made of copper.

In addition, since copper dihydroxide is a layered mineral, it has excellent adhesion to leaves and fruits of crops, and it is an ultrafine particle, which not only improves the efficiency of the drug by increasing the surface area, but also weakens by alkali because the pH of the suspension is near neutral. There is no effect is easy to mix with other drugs.

On the other hand, when the copper is prepared in the form of a copper dihydrate suspension according to the method of the present invention, there is an effect that can be prepared a suspension containing high concentration of ultra-fine particles of copper dihydrate crystal particles.

Figure 1a is a graph showing the change in the X-ray diffraction pattern of the copper dihydroxide prepared in Examples 1 to 5;
Figure 1b is a photograph showing a comparison of the dispersibility of each copper dihydroxide suspension prepared in Examples 1-5;
FIG. 2 is a graph showing changes in X-ray diffraction patterns of each of the copper dihydroxide and copper dihydroxide-organic acid prepared in Examples 6 to 8; FIG.
Figure 3 is a photograph showing the weak reaction of the cucumber according to the dilution factor of the copper dihydroxide suspension.

Crops for crops according to the present invention include a suspension of layered copper dihydroxide, wherein copper dihydroxide [Cu ₂ (OH) ₃ · X] is a crystallographically distinct two copper atoms of 4 + 2 (oxygen) The copper octahedron consisting of + X) and 5 + 1 (oxygen + X) is regularly arranged in a warped form, and the counter anion X present between the layers forms a direct coordination bond with the copper ion. It is a crystalline mineral. Therefore, it has a wide surface area, high anion exchange ability, shape memory effect, and thermal stability, and is used as a catalyst, ion exchanger, carrier, and conductor in various industrial fields.

In addition, the copper double hydroxide contains more than 50% of copper, has a layered structure similar to layered double hydroxides, high anion exchange capacity and high stability of the crystal structure, as well as a constant crystal, unlike lime bordea solution It is a mineral having a structure (Cdl ₂ ). Therefore, it has a structural characteristic that can minimize the disadvantages of the existing copper, and maximize the advantages of the inorganic agent.

Therefore, the copper double hydroxide can be used as a new high-performance copper material, which overcomes the problems of copper, including lime bordeaux liquid, and has high efficacy, efficiency, stability, dispersibility, and shelf life.

In addition, when an antimicrobial compound is introduced between the copper dihydroxide layers, the functional copper is further enhanced. As such an antimicrobial compound, it is useful to be selected from those which form -COO ^- like an organic acid having an carboxylic group or an amino acid containing a carboxyl group such as benzoic acid, cinnamic acid, salicylic acid, citric acid, butyric acid and propionic acid.

Copper for crops according to the present invention having such a configuration, anthrax, powdery mildew, late blight, brown algae, black rot, vine splitting disease, black pattern disease, wilting disease, red star pattern disease, burn disease, leaf organ disease, rust disease, Downy mildew, black spot disease, etc. can be used for the purpose of prevention and control, and in the fruit trees, downy mildew, rust disease, gray mold disease, black snow disease, spot pattern disease, red disease, leaf rot disease, anthrax disease, spot pattern disease, rhyme disease, black bean disease, black disease, red disease, white powder disease It can be effectively used for the purpose of prevention and control of round pattern disease, mosaic disease, branch disease, and the like.

Meanwhile, the copper for crops according to the present invention may be prepared by coprecipitation by adding an alkaline solution to a copper salt solution to form a copper dihydroxide by a reaction as shown by the following Chemical Formula 1.

That is, when a copper salt solution of high concentration is made and an alkali solution of high concentration is gradually added, a thin plate-like copper double hydroxide having positive charges is formed between layers, and the positive charges are introduced into the crystal interlayers. Neutralization enables the production of a suspension containing crystal grains of copper dihydroxide in the form of high concentrations of ultrafine particles.

In this case, as the copper salt, copper nitrate [Cu (NO ₃ ) ₂ ], cuprous chloride (CuCl), cupric chloride (CuCl ₂ ), copper sulfate (CuSO ₄ ), copper acetate [Cu (CH ₃ COOH) ₂ ], And copper perchlorate Cu (ClO ₄ ) ₂ ] may be used any one selected from the group consisting of or a mixture of two or more thereof, and the alkali agent forming the alkaline solution is sodium hydroxide (NaOH), potassium hydroxide ( KOH) and ammonia water (NH ₄ OH) may be used, or two or more thereof may be mixed and used.

On the other hand, in order to use the copper dihydroxide as a copper having a crop protection function, the amount of the alkaline solution is adjusted so that the final pH of the suspension is in the range of 5.5 to 7.0. If it is out of this pH range, there is a problem that the crystal size is greatly changed, or the viscosity and color of the suspension is rapidly changed by the production of copper oxide.

In addition, as the reaction temperature increases, the copper dihydroxide crystal size increases or forms a grain, so that the dispersibility of the suspension is relatively low, so that the reaction is gradually performed near room temperature.

Hereinafter, the copper for crops and the manufacturing method thereof according to the present invention will be described in detail through specific examples.

Example  1 ~ 5: having crop protection function Copper Dioxide  Manufacture of copper

3M sodium hydroxide solution was added to the 3M copper nitrate solution to adjust pH to 3.0 (Example 1), 4.5 (Example 2), 6.0 (Example 3), 9.0 (Example 4), and 11.0 (Example 5). Each was adjusted and stirred for 1 hour or more at room temperature to allow the reaction to occur.

The copper dihydride thus produced was dried at 80 ° C. for 24 hours to investigate crystallinity and dispersion of the suspension, and the results are shown in FIGS. 1A and 1B, respectively.

As shown in FIG. 1A, in the X-ray diffraction analysis, the intensity of the peak of 001 of 12.78 representing the crystallinity of the copper dihydroxide increased as the pH of the reaction solution increased, but rather decreased above pH 9.0.

In addition, the color and dispersibility of the copper dihydroxide suspension, as shown in Figure 1b, it is observed that at pH 3.0, the blue color due to the color of the upper portion of the suspension due to the hydrated copper form Cu (H ₂ O) ₆ ²⁺ is observed. In view, copper nitrate [Cu (NO ₃ ) ₂ ] was partially converted to copper dihydroxide, some of which was dissolved in water. However, it can be seen that when the pH of the reaction solution is higher than 4.5, copper nitrate is converted to copper dihydroxide.

In addition, the precipitate color of the copper dihydrate was light blue in the range of pH 3.0-6.0, but light brown at the pH 9.0 and dark brown at the pH 11.0 due to the formation of copper oxide (CuO). Therefore, the crystallinity and the dispersibility of the copper dihydroxide according to the pH of the reaction solution was confirmed to be the best at pH 6.0.

Example  6 to 8: Copper Dioxide Manufacture of Organic Copper

Copper dihydrate suspension (Example 6) was prepared under the conditions of copper nitrate and sodium hydroxide 3.0M, reaction temperature 25 ℃, ripening time 2 hours and the reaction solution pH 6.0.

After adding 5.0 w / v% of benzoic acid (Example 7) or cinnamic acid (Example 8), known as a natural antimicrobial agent, to the copper dihydroxide suspension in the form of a salt, the mixture was stirred for 12 hours so as to perform an ion exchange reaction. Copper made in organic acid form was prepared.

Then, X-ray diffraction analysis of the copper double-oxide oxide-organic acid copper thus prepared was shown in FIG. 2.

The benzoic acid ion-exchanged copper dihydroxide (Example 7) disappeared the main peaks of 6.9, 3.5 and 2.7 GHz, and produced new peaks at 15.7, 7.8 and 5.2 GHz and the cinnamic acid ion-exchanged copper dihydroxide (execution) Example 8) produced new peaks at 20.5, 10. 3. 6.8 and 3.4 Hz.

As a result of X-ray diffraction analysis, the interlayers of copper dihydroxide were expanded by ion exchange reaction of benzoic acid and cinnamic acid, and distinctive 001 , 002 and 003 peaks of layered minerals were observed. It was confirmed that was introduced stably.

Trial 1: weakening test for cucumbers

After sowing, the seedlings of 30 days old were transplanted into round pots of 10 cm diameter, 6 cm diameter and 9 cm height, and then stabilized cucumber seedlings for 7 days. The copper in the form of a suspension was treated with dilutions diluted 10, 25, 80 and 100 times, respectively, and examined for weakness while visually observing for 1 to 7 days. The results are shown in Table 1 and FIG.

division Days after drug treatment One 3 5 7 No treatment - - - - 10-fold dilution of copper dihydroxide - + ++ +++ 25-fold dilution of copper dihydroxide - - + ++ 50-fold dilution of copper dihydroxide - - + ++ Copper Dioxide 100-fold Diluent - - - -

※ Symptoms of weakness:-None, + Slightly, ++ Severe, +++ Very Severe.

No adverse symptoms were found in cucumbers treated with 100-fold dilutions of copper dihydroxide suspensions. However, in the 50-fold dilution treatment, very slight weakening occurred after 5 days of leaf tip drying. In the 25-fold dilution treatment treatment, the slight weakening occurred after 5 days, and after 7 days, the entire leaf was bent. There was a rather serious weakening in the dryness. In the 10-fold dilution treatment, weakening occurred from day 3, and after 7 days, the curvature of the leaves was intensified, causing severe whitening (Chlorosis).

This yellowing of cucumber leaves and stunting of leaf tip are typical symptoms caused by copper's weakness, and the weakening reaction by copper dihydroxide suspension may be slightly different depending on crops, but it is more than 100 times diluent. It has been shown that it is appropriate to handle.

Test 2: Effect of Melon Powder

250 times dilution of copper dihydroxide prepared in the same manner as in Example 6 before powder powder occurred in the facility house melon, 100 times, 250 times, and 500 times the copper dihydroxide-cinnamic acid prepared in the same manner as in Example 8. Dilution, 50-fold dilution of lime Bordeaux solution, and 2,000-fold dilution of commercial synthetic pesticides were treated with melon, respectively, and after 15 days, the incidence and control value of powdery mildew were investigated. The results are shown in Table 2.

division
Incidence of powdery mildew (%) Control (%)
1 repetition 2 repetitions Average Synthetic pesticide 2,000 times dilution 0.5 0.8 0.7 79.2 Lime Bordeaux liquid 40-fold dilution 0.3 0.3 0.3 91.7 250 times copper double hydroxide 0.5 0.3 0.4 87.5 Copper Dioxide-Cinnamic Acid 100-fold Diluent 0.3 0.3 0.3 91.7 Copper Dioxide-Cinnamic Acid 250 Times Dilution 0.5 0.3 0.4 97.5 Copper Dioxide-Cinnamic Acid 500 Times Dilution 0.3 0.3 0.3 91.7 No treatment 3.0 3.0 3.0 -

In the melon field with 0% incidence of initial powdery mildew, the average area area of the untreated group after 15 days was 3.0%. The average control values of synthetic pesticides and lime bordeaux solution in control were 79.2% and 91.7%, respectively. In addition, the control value of the copper double hydroxide 250 times, copper double hydroxide-cinnamic acid 100 times, 250 times, 500 times treatment treatments showed a similar tendency to the dilution of lime Bordeaux solution as 87.5%, 91.7%, 97.5%, 91.7%, respectively.

As a result, copper dihydroxide and copper dihydroxide-cinnamic acid were similar or superior to the existing drugs as a preventive agent to treat before the powdery melon disease.

Test 3: Controlling Powder Powder of Melon

In order to investigate the control effect of powdery melon powder, 250 times dilution of copper dihydroxide prepared in the same manner as in Example 6, copper prepared in the same manner as in Example 6, in a melon package having a powdery mildew incidence of 16.2% The powder incidence and control value were investigated 10 days after treatment with 100-fold, 250-fold dilution of dihydroxide-cinnamic acid, 50-fold dilution of lime Bordeaux solution and 2,000-fold dilution of commercial synthetic pesticides, respectively, and the results are shown in Table 3.

division Incidence of powdery mildew (%) Control is (%)
1 repetition 2 repetitions 3 repetitions Average Synthetic pesticide 2,000 times dilution 3.5 4.0 3.3 3.6 77.8 50-fold dilution of lime Bordeaux solution 0.8 1.3 1.5 1.2 92.8 250x Dilution of Copper Dioxide 1.0 0.8 1.5 1.1 93.3 Copper Dioxide-Cinnamic Acid 250 Times Dilution 1.0 1.8 1.5 1.4 91.7 Copper Dioxide-Cinnamic Acid 100-fold Diluent 0.3 0.8 1.8 0.9 94.3 No treatment 23.5 27.4 21.8 23.5 -

The average incidence of powdery mildew in untreated groups was 23.5%, an increase from 16.2% 10 days ago. The control values of the synthetic pesticides and lime Bordeaux diluents were 77.8% and 92.8%, respectively.

In addition, the control values of the copper dihydrate 250 times dilution, copper dihydroxide-cinnamic acid 100 times, and 250 times dilution treatment treatment were 93.3%, 91.7%, and 94.3%, respectively, which were similar to or slightly superior to the existing powdery mildew control agents. However, as shown in the results of the preventive effect (Table 2), there was no obvious synergistic effect due to the introduction of organic acid into the copper dihydroxide, and since there was little significance according to the dilution factor, the dilution factor of the copper dihydroxide suspension was 250 times or more. This appeared to be appropriate.

Test 4: Copper  Copper content comparison

Self-manufactured lime bordo liquid, domestic lime bordo liquid, domestic lime bordo liquid and copper bicarbonate prepared in the same manner as in Example 6, copper double hydroxide prepared in the same manner as in Example 8 Table 4 shows the results of analyzing the copper concentrations of the stock solution and the diluted solution of hydroxide-cinnamic acid, respectively.

Kind of copper Stock Solution Cu Concentration
(%) Dilution factor
(ship) Diluent Cu Concentration
(Mg / l) Diluent pH
Lime Bordeaux liquid self-production (6-6 meals) - - 1,525 > 12.0 Domestic lime Bordeaux liquid 1.85 40-50 411 12.2 Japanese Lime Bordeaux Liquid 4.52 50-100 602 12.3 Copper Dioxide 7.12 250 285 6.0 Copper Dioxide-Cinnamic Acid 6.71 250 268 6.3

The copper content of the most commonly used 6-6 type lime bordea solution (diluent) produced by farmers was very high as 1,525 mg / l. In addition, the copper content of the lime Bordeaux solution, which is specially manufactured and sold in Korea, and the imported commercial lime Bordeaux solution, were 1.85% and 4.52%, respectively. And the copper concentration of domestic and Japanese lime Bordeaux diluent sprayed to the crop was 411 ~ 602㎎ / ℓ. As such, the commercial lime Bordeaux stock solution produced in Korea and Japan has a low copper content, so that the dilution factor is only 40 to 100 times, and the packaging unit of the product is 5 to 20 liters, which is inconvenient for transportation, storage and use. Is given.

On the other hand, the copper concentrations of the copper dihydroxide and copper dihydroxide-cinnamic acid suspensions according to the present invention were 7.12% and 6.71%, respectively, 1.58 to 3.85 times higher than those of commercial lime bordea solution. As a result of the above test results, the minimum dilution factor of the copper dihydroxide was 250 times or more, so the copper concentrations of the copper dihydroxide and the copper dihydroxide-cinnamic acid dilution were 285 and 268 mg / L, respectively, which were lower than those of the commercial lime bordea solution. In other words, the copper concentrations of the copper dihydroxide and copper dihydrogen coral-cinnamic acid diluents were 5.35-5.69 times lower than those of the 6-6 lime bordeaux solution and 1.44-2.25 times lower than those of the commercial lime bordeaux solution. Therefore, in the copper according to the present invention, since the copper concentration of the copper dihydrate diluent is low, the treatment concentration of copper per unit area is lower than that of the conventional lime bordeaux solution, which can improve the problems of copper accumulation for crops and soils. It is expected to be used as a brother-in-law preparation.

In addition, as shown in Table 4, according to the method of the present invention, it is possible to produce a high concentration of copper dihydroxide suspension with a higher copper content than the lime bordeaux solution, it is judged to be excellent in economic efficiency and applicability.

Trial 5: Controlling Strawberry's Gray Mold Disease

In order to investigate the crop control effect of copper double hydroxide copper, 250-fold dilution of copper dihydroxide prepared in the same manner as in Example 6, 50-fold dilution, which is the proper use range of lime bordeaux solution, to strawberries with gray mold disease, and A 500-fold dilution of synthetic pesticides was treated after 50 days, and the incidence rate and control value were investigated after 10 days, and the results are shown in Table 5.

division Control effect Incidence (%) Control (%) No treatment (common cultivation) 25.4 0 50-fold dilution of lime Bordeaux solution 6.9 64.0 500-fold dilution of synthetic commercial pesticides 6.3 75.2 250x Dilution of Copper Dioxide 7.1 74.9

As shown in Table 5, the gray mold control value of strawberries treated with copper dihydroxide was 74.9%, 10% higher than that of lime bordeaux solution, and showed a control value almost similar to that of synthetic pesticides. Therefore, it was confirmed that the treatment of gray mold, which is known to be difficult to control in strawberry cultivation farms, can be effectively controlled by the treatment of copper dihydroxide.

Claims (7)

A crop copper, comprising a suspension of a layered copper dihydroxide. The crop copper agent according to claim 1, wherein an antimicrobial compound selected from organic acids having a carboxyl group or amino acids having a carboxyl group is introduced between the copper dihydroxide layers. delete The crop copper according to claim 1, wherein the suspension has a pH in the range of 5.5 to 7.0. A method for producing a crop copper, comprising the step of preparing a suspension of a layered copper dihydroxide by adding an alkali solution to a copper salt solution and coprecipitation. The copper for crops according to claim 5, wherein the copper salt is any one or two or more selected from the group consisting of copper nitrate, cuprous chloride, cupric chloride, copper sulfate, copper acetate, and copper perchlorate. Preparation method of the agent. The method of claim 5, wherein the alkali solution is a method for producing copper for crops, characterized in that any one or two or more selected from the group consisting of sodium hydroxide solution, potassium hydroxide solution, and ammonia water is mixed.

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