JP2003267810A - Disinfecting and mineral-replenishing agent for agriculture and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new agrochemical free from toxicity or having low toxicity and performing the disinfection of soil simultaneously with the improvement of the soil by replenishing essential minerals. <P>SOLUTION: The disinfecting and mineral replenishing agent for agriculture contains at least one kind of solid-solution expressed by formula (1), (2), (3) or (4) as an active component. (M<SB>1</SB>)<SP>2+</SP><SB>1-x-y</SB>(M<SB>2</SB>)<SP>2+</SP><SB>x</SB>(M<SB>3</SB>)<SP>2+</SP><SB>y</SB>O...(1); (M<SB>1</SB>)<SP>2+</SP><SB>1-x-y</SB>(M<SB>2</SB>)<SP>2+</SP><SB>x</SB>(M<SB>3</SB>)<SP>2+</SP><SB>y</SB>(OH)<SB>2</SB>...(2); [(M<SB>1</SB>)<SP>2+</SP>,(M<SB>2</SB>)<SP>2+</SP>,(M<SB>3</SB>)<SP>2+</SP>]<SB>1-z</SB>(M<SP>3+</SP>)<SB>z</SB>O...(3); and [(M<SB>1</SB>)<SP>2+</SP>,(M<SB>2</SB>)<SP>2+</SP>,(M<SB>3</SB>)<SP>2+</SP>]<SB>1-z</SB>(M<SP>3+</SP>)<SB>z</SB>(OH)<SB>2</SB>A<SP>n-</SP><SB>z/n</SB>.mH<SB>2</SB>O...(4) (M<SB>1</SB>and M<SB>2</SB>are each a specific bivalent metal; M<SP>3+</SP>is a specific trivalent metal; A<SP>n-</SP>is an n-valent anion; and (x), (y), (z) and (m) are numbers falling within respectively specific ranges). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a novel non-toxic or low-toxic, multifunctional agricultural product which has no phytotoxicity, can rejuvenate plants and enhance resistance to diseases, and can supplement and sterilize minerals. The present invention relates to a bactericidal / mineral supplement and a method for producing the same.

[0002]

2. Description of the Related Art Conventional agricultural fungicides are mainly organic, and there are many types of organic fungicides, which generally have excellent medicinal effects.
On the other hand, however, it is highly toxic and has a wide range of versatility due to its strong drug selectivity. On the other hand, an inorganic copper agent containing copper hydroxide or basic copper sulfate as an active ingredient as an inorganic type has a medicinal effect which is not so remarkable as an organic type, but has low toxicity, is effective for most diseases, and cannot be tolerated. , Is an extremely old product,
It is still widely used today. The low toxicity of this inorganic copper agent can be understood from the fact that its use is permitted even in organic (organic cultivation) where the use of pesticides is prohibited.
However, since inorganic copper agents have phytotoxicity such as crop deterioration, and are themselves insoluble in water and acidic,
There is a problem that the drug is deposited on the soil surface and the soil is acidified, and the crop yield is reduced year by year.

The present inventor has previously proposed, as a novel agricultural fungicide, Cu ²⁺ and / or Zu ^{2 +} , a compound obtained by individually dissolving a hydroxide of Mg and / or Ca or an oxide, or Cu ^2+. An oxide in which trivalent Al, Fe and the like are individually dissolved in an oxide of and / or Zn ²⁺ has been proposed (Japanese Patent Laid-Open No. 08-048606). These compounds are low-toxic or non-toxic and do not cause the problem of acidifying the soil by being deposited on the soil surface after being sprayed.

[0004]

Problems of toxicity of pesticides on plants and animals including human beings are being recognized, and in recent years,
Farmers producing organic products that use neither pesticides nor fertilizers are expanding in developed countries. However, organic production generally requires more effort and yields less than using pesticides.

Therefore, the present invention is a novel agricultural fungicide having high medicinal effect, which has a lower toxicity than that of lime bordeaux and which does not cause the problem of soil acidification, which is a drawback of lime bordeaux, which can be used for organic purposes. For the purpose of providing. Further, the present invention aims to provide a method for producing such an agricultural fungicide.

[0006]

The present invention provides the following formulas (1) to (1)
(4)   (M₁)²⁺ _1-xy(M_Two)²⁺ _x(M_Three)²⁺ _yO (1)   (M₁)²⁺ _1-xy(M_Two)²⁺ _x(M_Three)²⁺ _y(OH)_Two  (2)   [(M₁)²⁺, (M_Two)²⁺, (M_Three)²⁺]_1-z(M³⁺)_zO (3)   [(M₁)²⁺, (M_Two)²⁺, (M_Three)²⁺]_1-z(M³⁺)_z(OH)₂A^{n −} _{z / n} ・ MH_TwoO (4) (However, in the formula, M₁Is Mg and / or Ca, M_TwoIs
Cu and / or Zn is replaced by M_ThreeIs M₁And M_TwoExcluding
The essential minerals that always contain Mn and Fe are M ³⁺Is
Al³⁺And / or Fe³⁺, Cr³⁺, C
o³⁺, Mn³⁺, B^{Three +}At least selected from
One or more essential minerals, A^n-Is No_Three ⁻, HP
O_Three ^2-, CO_Three ^2-, SO_Four ^2-N-valent anions such as
Where x, y, z and m are in the following ranges, 0 <
x <0.5, 0 <y <0.5, 0 <x + y <0.5, 0
<Z <0.4, the number satisfying 0 ≦ m <4 is shown)
Oxides containing essential minerals as main components and / or
Agriculture characterized by containing hydroxide as an active ingredient
We provide industrial germicides and mineral supplements.

Further, the present invention provides a production method using seawater or concentrated bitter juice containing all essential minerals as a raw material for synthesizing the compounds of the formulas (1) to (4).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies, the present inventor has found that, in order to exert a high level of bactericidal activity even though it is a target compound with high safety, it has two functions: prevention against bacteria and sterilization. We came to think that it would be possible to have both at the same time. Based on this idea, as a result of further exploration, a calcium hydroxide-based solid solution, a magnesium oxide-based solid solution and a hydrotalcite compound-based bactericide invented by the present inventors or an oxide solid solution-based bactericide obtained by firing thereof, We have arrived at a method for solid solution of essential mineral components such as iron and manganese that are effective for plant growth.
And, it was discovered that the compound synthesized based on this idea exerts the expected result.

Since the agricultural fungicide and mineral supplement of the present invention is an alkaline oxide or hydroxide,
It is insoluble in water, but has the characteristic that it easily dissolves in water on the order of ppm level. The compound of the formula (2) of the present invention is a compound having the same crystal structure as calcium hydroxide and / or magnesium hydroxide, and the compound of the formula (1) allows them to be about 400 ° C. or higher, preferably about 500 to 1000 ° C. It is an oxidized solid solution formed by firing at.

The compound of the formula (2) is prepared by using a mixed aqueous solution of M ₁ and M ₂ and an alkali such as sodium hydroxide.
It can be produced by a method of coprecipitation at a pH of about 8 or higher, preferably about 10 to 13. The compound of formula (1) has the formula (2)
It can be obtained by calcining the compound (1) at about 400 to 900 ° C.

The compound of formula (4) is a compound belonging to the hydrotalcite class. The compound of formula (3) is most often obtained by calcining the compound of formula (4) at about 200 ° C or higher, preferably about 400-900 ° C.
The compound of formula (4) can be prepared by (M ₁ ) ²⁺ , (M ₂ )
^It can be carried out by a method in which a mixed aqueous solution of ²⁺ and (M ₃ ) ²⁺ and M ³⁺ is coprecipitated with an alkaline aqueous solution at a pH of about 7 or more. The compounds of formula (3) and formula (4) have M ²⁺
And M ^{3+ is} an oxide solid solution or a hydroxide solid solution.

The compounds of the formulas (1) to (4) used in the present invention are dispersed in water and sprayed on crops. Most preferred are wettable powders and suspensions. In addition to this, of course, a powdery material can also be sprayed.

The concentration of the mineral supplement and fungicide of the present invention as a wettable powder is about 10 ppm or more, preferably about 50 to about 50 ppm.
It is in the range of 2000 ppm.

The compounds of the formulas (1) to (4) used in the present invention are easily dispersed in water, and it is preferable to disperse them in the form of fine particles. In order to meet such conditions, those having an average secondary particle diameter of at least 2 μm or less, preferably 1 μm or less, and particularly preferably 0.5 pm or less are used. In order to produce the compound of the present invention having a particle size in an appropriate range, fine pulverization treatment such as wet ball mill pulverization is preferably adopted in addition to optimization of synthesis conditions. Further, surface treatment with an anionic or nonionic surfactant can be applied.

Furthermore, in order to facilitate and simplify the handling of the agricultural worker, reduce the burden on the worker, maximize the sterilizing effect, and increase the reproducibility of the spraying effect, the above-mentioned method, etc. It is preferable to supply the finely-divided compound of the present invention prepared in step (1) to the operator side in a concentrated liquid or cake form without drying. The worker simply replenishes the concentrate or cake with water with stirring, and the fine particles are well dispersed. The agent can be obtained. On the other hand, when dry powder is used, even if it is fine particles itself, in order to disperse water in the original level of fine particles, a strong dispersion treatment such as strong ultrasonic treatment or homogenizer treatment is used. , And in practice it is difficult to use such a device on a farm.

The agricultural fungicide / mineral supplement of the present invention may be in the form of a suspension, a wettable powder, a powder or the like as described above. At that time, if necessary, a surfactant, a dispersant, a filler, etc. may be used in combination. Specific examples of the surfactant and the dispersant are as follows. Lignin sulfonates, polycarboxylates, (alkyl) naphthalene sulfonates and their condensates, phenol sulfonic acid hydrochlorides and their condensates, styrene sulfonates and their condensates, maleic acid and styrene sulfonic acid condensates , An alkylbenzene sulfonate, a dialkyl sulfosuccinate, a salt of polyoxyethylene alkyl ether sulfate, a salt of polyoxyethylene alkyl allyl ether phosphate, and an anionic surfactant and a dispersant. Examples of the filler include bentonite, zeolite, talc, aluminum silicate, clay, diatomaceous earth, amorphous silicon dioxide, calcium urate and magnesium carbonate.

The agricultural fungicide / mineral supplement of the present invention is effective against a wide range of pathogenic fungi, and has the medicinal damage found in conventional copper agents and the yield of crops over a long period of time due to the acidity of soil. There is no problem of deterioration.

The crops and diseases for which the agricultural fungicide and mineral supplement of the present invention are particularly effective include, for example, downy mildew of grapes, gray mold of pepper, sugar beet of sugar beet, blast of rice and blast of rice. Sesame leaf blight, plague of tomato, downy mildew of cucumber, downy mildew of olive, red rust of wheat,
Tomato phosphorus disease etc. can be mentioned.

As a spraying method, a conventional method such as a human power injector, a power injector, a mist machine, a speed sprayer and an aerial sprayer can be appropriately adopted. Hereinafter, the present invention will be described in more detail based on examples.

[0020]

EXAMPLE 1 Calcium chloride, magnesium chloride converted magnesium sulfate to magnesium chloride by the addition of calcium chloride, bitter broth produced by the salt process (manufactured mainly by magnesium chloride, and other essential minerals derived from seawater, such as Mn,
Mo, Se, Co, etc.), ferrous chloride, manganese chloride, cupric nitrate mixed aqueous solution (Ca = 0.87 mol / liter, Mg = 0.05 mol / liter, Fe ²⁺ = 0.0
(05 mol / liter, Mn ²⁺ = 0.005 mol / liter, Cu ²⁺ = 0.07 mol / liter, respectively)
0.4 l of air was replaced with nitrogen gas under stirring,
With flowing nitrogen gas, at about 30 ° C. for about 2 minutes, 0.
The total amount was added to a three-necked flask containing 0.4 liter of an aqueous solution of 824 mol of sodium hydroxide and reacted. The reaction product slurry was filtered in a nitrogen atmosphere, washed with water, placed in a ball mill, and treated in a nitrogen atmosphere with zirconia balls having a diameter of 0.5 mm for 2 hours. After the treatment, it was concentrated in a centrifugal separator to a solid content concentration of about 15% by weight.

A portion of this was probed and lyophilized, and the BET specific surface area was measured by X-ray diffraction, chemical analysis, laser diffraction particle size distribution, and liquid nitrogen adsorption method. The X-ray diffraction pattern was only that corresponding to calcium hydroxide. As a result of chemical analysis, the chemical composition was Ca _0.87 Mg _0.05 Fe _0.005 Mn.
_{It was 0.005} Cu _0.07 (OH) ₂ . As for the particle size distribution, the average secondary particle diameter with a cumulative 50% was 0.86 μm. BET specific surface area is 15 m ² / g
Met.

[0022]

[Example 2] A mixture of sun salt method bitter broth, ferrous sulfate, manganese chloride and cupric nitrate (Mg ²⁺ = 0.9 mol / l, Fe ²⁺ = 0.03 mol / l, Mn
²⁺ = 0.02 mol / liter, Cu ²⁺ = 0.05 mol / liter, respectively) 10 liters and 2 mol / liter sodium hydroxide, using a metering pump to obtain a volume of 3
Approximately 100 m in each round reaction tank with a stirrer
It was supplied at 1 / min and 105 ml / min, but the reaction was carried out at a temperature of about 40 ° C. under a nitrogen atmosphere while adjusting the pH to about 11.5 with the flow rate of sodium hydroxide. The reaction product slurry was filtered in a nitrogen atmosphere, washed with water, and dried. The dried product was crushed. Firing was performed at 750 ° C. for 2 hours in a nitrogen atmosphere in an electric furnace. The X-ray diffraction pattern of the baked product was only magnesium oxide. As a result of the chemical analysis, the chemical composition was Mg _0.90 Fe _0.03 Mn _0.02 Cu _0.05 O 2. Regarding the particle size distribution, the average secondary particle diameter of cumulative 50% was 1.2 μm, and the BET specific surface area was 31 m ² / g.

[0023]

Example 3 A mixed aqueous solution of zinc chloride, ferric chloride and manganese chloride (Zn ²⁺ = 0.92 mol / liter, Fe ³⁺
= 0.06 mol / l, Mn ²⁺ = 0.04 mol /
Liter) and a 4 mol / liter aqueous solution of sodium hydroxide in a round reaction tank equipped with a stirrer with a volume of 3 liters using a metering pump at about 100 ml / min and about 52 ml, respectively.
The reaction was conducted by adjusting the pH to about 10 and adjusting the temperature to about 30 ° C. with the flow rate of sodium hydroxide. The slurry obtained by the reaction was filtered under reduced pressure, washed with water, dried, pulverized, put in an electric furnace and fired at about 500 ° C. for 1 hour. The X-ray diffraction pattern of the baked product was only zinc oxide. As a result of the chemical analysis, the chemical composition was Zn _0.90 Fe ³⁺ _0.06 Mn ³⁺ _0.04 O 2. Regarding the particle size distribution, the average secondary particle diameter of cumulative 50% was 0.76 μm, and the BET specific surface area was 35 m ² / g.

[0024]

[Example 4] Zinc chloride, sun salt broth, ferric chloride,
Mixing an aqueous solution of manganese chloride ^(Zn 2 + = 0.8 mol / ^liter, Mg 2+ = 0.05 mol / l, ^{Fe 3+}
= 0.1 mol / liter, Mn ²⁺ = 0.05 mol / liter) and 4 mol / liter of an aqueous solution of sodium hydroxide using a metering pump in a round reaction tank with a stirrer having a capacity of 3 liters, each having about 100 ml. / Min, about 50ml /
However, the reaction was carried out at a temperature of about 30 ° C. while adjusting the pH to about 7.4 with the flow rate of sodium hydroxide. After the reaction product is filtered, washed with water, dried and crushed, 400
Calcination was performed for 1 hour. The X-ray diffraction pattern of the fired product was slightly shifted to the higher angle side, but was the same as that of zinc oxide.
As a result of the chemical analysis, the chemical composition was (Zn _0.80 Mg _0.05 ) ²⁺ (Fe _0.10 Mn
_0.05 ) ^{3 +} O. Regarding the particle size distribution, the average secondary particle diameter of cumulative 50% was 0.86 μm, and the BET specific surface area was 36 m ² / g.

[0025]

Example 5 The fungicidal and mineral supplements obtained in Examples 1 to 4 were each diluted with water to adjust the concentration to 2000 ppm. To enhance spreadability, sorbitan monolaurate as a surfactant was added to the slurry so as to be 20 ppm. Using a hand spray,
Koshihikari was grown in a cup with a diameter of 10 cm and a depth of 4 cm, and about 1 cup per cup was obtained for the rice in the third leaf extraction stage.
0 ml was sprinkled. After the chemical solution was dried, the rice treated with the chemical solution had about 30 spores of the blast fungus spores under a microscope with a field of view of 150 times.
About 5 ml of each inoculum was spray-inoculated with a hand spray of an inoculum prepared by individually adding sorbitan monolaurate in an amount of 5000 times. This was managed under high temperature (30 ° C.) conditions in a glass chamber, and the number of diseased lesions on the second leaf was measured for 30 strains per treatment group on the 7th day after inoculation, and 1
The average number of diseased spots per strain (development) was calculated, and the control value was calculated by the following formula.

Control value = (average value of disease rate in untreated plot-average value of disease severity in treated plot) / (average value of disease incidence in untreated plot) Table 1 shows the results.

[0027]

[Table 1]

[0028]

Example 6 The fungicidal / mineral replenishers obtained in Examples 1 and 2 were diluted to adjust the concentration to 1000 ppm. 50% of the spreading agent Tween-20 was added to this slurry.
It was added so that it would be diluted to 100 times. Using a hand spray, this chemical solution was sprayed on tomatoes grown at the 10th leaf stage to such an extent that the chemical solution drips. The tomato treated with the chemical solution was inoculated by the following method on the same day after the chemical solution was completely dried.

Suspended zoospores of tomato disease fungus in water,
The zoospores were released and used as an inoculum. Twe to this inoculum
After adding en-20 at a 5000-fold dilution, it was inoculated by hand spray at a rate of about 5 ml per strain. The inoculated tomatoes were placed in a thermostat at 25 ° C. and a humidity of 100% in the dark, kept for 24 hours, and then managed in a glass greenhouse. Six days after the inoculation, the degree of disease on the third compound leaf to 7 leaves of each strain was evaluated, the disease severity was calculated, and the control value was calculated.

Disease severity = Σ (number of diseased leaves by degree × index) /
(Number of surveys x 4) x 100 Control value = (average value of disease rate of untreated plot-average value of disease severity of treated plot) / (average value of disease severity of untreated plot) Index 0: Disease on compound leaves Not observed at all: 1: 1 disease area ratio per compound leaf is less than 5% 2: 1 disease area ratio per compound leaf is 5% to 25% 3: 1 disease area ratio per compound leaf is 25% to 50% 4: 1 compound leaf The diseased area rate per hit exceeds 50%, and the results are shown in Table 2.

[0031]

[Table 2] Test results for tomato epidemic

[0032]

Example 7 Powder of the compound obtained in Examples 1 to 1.0
g was added to 500 ml of deionized water, shaken well by hand to mix, and then left overnight at room temperature. The next day, the solution was filtered, the filtrate was collected, and the eluted mineral ions (Fe, Mn, Cu, Z
n) The concentration was measured by the atomic absorption method. The results are shown in Table 3.

[0033]

Comparative Example 1 Cupric hydroxide [Cu (O
H) ₂ ], zinc oxide [ZnO], ferric oxide [Fc]
₂ O ₃ ], manganese oxide [MnO ₂ ] powder was used to measure the elution amount of mineral ions in water by the same method as in the example. The results are shown in Table 3.

[0034]

[Table 3] Elution amount of minerals in water

From the above results, F which is an essential mineral
In the case of e, Mn, Cu and Zn of the present invention, the elution properties in water are remarkably improved as compared with the single compounds of these minerals. Therefore, it can be considered that the absorptivity of minerals by agricultural products is significantly improved by using the compound of the present invention.

[0036]

INDUSTRIAL APPLICABILITY According to the present invention, an agricultural fungicide and a mineral which are nontoxic to low toxicity and have a high medicinal effect and are free from phytotoxicity, but which can supplement the essential mineral deficiency of iron and manganese in soil. Supplements are provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C05D 3/00 C05D 3/00 5/00 5/00 9/02 9/02 11/00 11/00 C05G 3/02 C05G 3/02 F term (reference) 2B022 AA01 AB13 AB15 AB20 EB10 4H011 AA01 BA01 BB18 BC08 BC18 DA13 DD03 DE16 DG06 4H061 CC01 CC15 CC21 CC24 DD07 DD11 EE13 EE14 EE15 EE16 EE17 EE19

Claims (7)

[Claims] 1. The following formulas (1), (2), (3) or
(4)   (M₁)²⁺ _1-xy(M_Two)²⁺ _x(M_Three)²⁺ _yO (1)   (M₁)²⁺ _1-xy(M_Two)²⁺ _x(M_Three)²⁺ _y(OH)_Two  (2)   [(M₁)²⁺, (M_Two)²⁺, (M_Three)²⁺]_1-z(M³⁺)_zO (3)   [(M₁)²⁺, (M_Two)²⁺, (M_Three)²⁺]_1-z(M³⁺)_z(OH)₂A^{n −} _{z / n} ・ MH_TwoO (4) (However, in the formula, M₁Is Mg and / or Ca, M_Two
Is Cu and / or Zn, and M_ThreeIs M₁And M_TwoTo
Excludes essential minerals that always include Mn and Fe³⁺
Is Al³⁺And / or Fe³⁺, Cr³⁺, Co
³⁺, Mn³⁺, B ³⁺At least one selected from
A or more essential minerals^n-Is No_Three ⁻, HPO
_Three ^2-, CO_Three ^2-, SO_Four ^2-N-valent anions such as
Where x, y, z and m are in the following ranges respectively, 0 <x
<0.5, 0 <y <0.5, 0 <x + y <0.5, 0 <
z <0.4, the number satisfying 0 ≦ m <4 is shown)
Oxides and / or water containing essential minerals as main components
Agriculture characterized by containing oxides as active ingredients
Disinfectant and mineral supplement. 2. The agricultural fungicide according to claim 1, wherein (M ₃ ) ^{2+ in} the formulas (1) to (4) according to claim 1 is Mn ²⁺ and Fe ^2+. Mineral supplement. 3. In the formula (1) according to claim 1, (M
₁ ) ²⁺ is Mg ²⁺ and (M ₂ ) ²⁺ is Cu ²⁺ , The agricultural fungicide / mineral supplement. 4. In the formula (2) according to claim 1, (M
₁ ) ²⁺ is Ca ²⁺ , and (M ₂ ) ²⁺ is Cu ²⁺ . The agricultural fungicide / mineral supplement according to claim 1. 5. The agricultural fungicide / mineral supplement according to claim 1, wherein (M ₂ ) ^{2 +} in formulas (3) and (4) according to claim 1 is Zn ²⁺ . 6. An agricultural bactericidal agent / mineral replenishing agent, which is prepared by dispersing the agricultural bactericidal agent / mineral replenishing agent according to any one of claims 1 to 5 in water or in a powder form and sprayed on the crop and its periphery. how to use. 7. The agricultural solution according to claim 1, wherein an aqueous solution of bitter juice in which seawater is concentrated is used as the M ₁ component of the synthetic raw material for the compound of formulas (1) to (4) according to claim 1. A method for producing a germicide and mineral supplement.