JPH0446106A - Fungicidal composition for agriculture and horticulture - Google Patents

Abstract

PURPOSE:To obtain the title composition having an antimicrobial or fungicidal film of aluminosilicate in which a metal ion having antimicrobial action is retained on the matrix surface of silica gel and/or alumina, having high antimicrobial or fungicidal activity and reduced in toxicity. CONSTITUTION:The aimed fungicidal composition for agriculture and horticulture having an antimicrobial or fungicidal film of crystalline and/or amorphous aluminosilicate having antimicrobial action in which one or more kind of metal ions, preferably selected from silver, copper, zinc and tin on the matrix surface of one or more kind of inorganic compounds selected from silica gel and alumina and having high antimicrobial or fungicidal activity and capable of exhibiting effects enough to plant disease damage at low chemical amount and simultaneously hardly exhibiting phytotoxicity to a plant.Furthermore, one or more kind of metals selected from further K, Ca, Mo, Mg, Zn, Mn, Ti, Co, Ni, Cu and/or Fe may be contained in the above-mentioned matrix and/or the above-mentioned film.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a 11Wi artistic fungicide that has preferable antibacterial activity against plant pathogenic bacteria and plant pathogenic bacteria. This is considered to be more desirable. More specifically, the present invention relates to the matrix surface (pores and macropores) of silica gel or alumina.
The present invention relates to a novel bactericidal composition for agricultural and horticultural use, which is characterized by having an antibacterial or bactericidal film of aluminosilicate that stably retains metal ions having a bactericidal effect.

In the field of conventional agricultural and horticultural technology, various pesticides such as fungicides, herbicides, and insecticides have been used, but their toxicity (for example, carcinogenicity) has become a problem, and recently, environmental pollution has become a problem. has become a problem, and the removal of pollutants such as toxic pesticides and countermeasures for contaminated wastewater have become social issues. For example, at golf courses, various organic pesticides are used to protect the grass and trees.
Approximately 2 tons are used per year per year, and the environmental pollution caused by this is causing social problems. Traditionally, copper-containing Bordeaux liquid has been used to control various diseases of vegetables, fruit trees, sulfur vegetables, etc., but this solution does not always have satisfactory efficacy or the range of diseases targeted is limited. It has the disadvantage that the range of use is limited because it is narrow and may cause phytotoxicity to crops.

In view of the above circumstances, in the field of agriculture and horticulture, there is little phytotoxicity,
There is an urgent need to develop fungicides that have high antibacterial or bactericidal activity when used in small quantities and are less toxic.

As an inorganic agricultural and horticultural fungicide,
As seen in No. 64 and JP-A-1-156905,
It is known that the skeleton is made of 5i-0-AZ (aluminosilicate) and copper ions etc. are bonded to it.

However, the pores (microbore) in the backbone of these disinfectants are extremely small, and therefore the release of germicidal metal ions takes a long time, resulting in insufficient contact with pathogenic bacteria and the effective utilization of germicidal metals. There is a disadvantage that the value decreases.

In order to obtain a satisfactory antibacterial or bactericidal effect, it was necessary to increase the pore diffusion rate of bactericidal metal ions by increasing the amount of bactericidal metal contained therein. Taking such measures does not lead to a reduction in the amount of drugs used. In view of the above facts, it cannot be said that the known inorganic killing agents are necessarily satisfactory.

Problems to be Solved by the Invention The object of the present invention is to provide a fungicide for agriculture and horticulture that has high antibacterial or bactericidal activity, exhibits sufficient effects even when used in low doses, and has low toxicity.

Means for Solving the Problems The present inventors have developed a method using silica gel or alumina as a matrix,
The antibacterial or bactericidal composition having an antibacterial or bactericidal film of aluminosilicate holding metal ions having a bactericidal effect through ionic bonds on the surface of the matrix has high antibacterial activity;
The present invention was completed based on the discovery that it is effective against plant diseases and causes almost no phytotoxicity.

The details of the present invention will be explained above.

For agricultural and horticultural purposes, the matrix is at least one inorganic substance selected from the group of silica gel and alumina, and has an antibacterial or bactericidal film of aluminosilicate containing metal ions having a bactericidal effect on the surface of the matrix. The present invention provides a bactericidal composition. The above-mentioned antibacterial or bactericidal film is made of crystalline and/or amorphous aluminosilicate, and the film performs a chemical reaction on the porous silica gel or alumina matrix surface (pores and macropores). It is formed stably. Further, as the metal ion having a bactericidal effect, at least one metal ion selected from the group consisting of silver, copper, zinc and tin is used.

That is, a composite of one or more metal ions selected from the metal group mentioned above replaces the ion-exchangeable metal in the film and is stably retained in the film.

The fungicidal composition for agricultural and horticultural purposes of the present invention having the above-mentioned structure is
For example, it has been found that it is highly effective in controlling various diseases of vegetables, fruit trees, bush crops, plants, etc., and since only a small amount is required, phytotoxicity is significantly improved. Furthermore, the present rule is expected to be fully applicable to crop fields, where the use of conventional fungicides such as Bordeaux liquid has been restricted, as they are less toxic.

The fungicidal composition for agriculture and horticulture of the present invention is
iacoli, 5taphyIococcus
aureus, Pseudomonas aerug
General bacteria such as S. inosa and Spergillus n.
jger+ AspergHlus flavus etc. true+! This invention not only exhibits excellent antibacterial or bactericidal effects against fungi (molds), but also has favorable effects against many plant pathogenic bacteria and plant pathogenic bacteria, so the antibacterial spectrum of this invention is wide-ranging. bactericidal composition of 0.01
Measurement of antibacterial activity against plant pathogenic bacteria using a suspension containing ~1% (medium PDA (Potato Dextros))
e Agar); After culturing at 25°C for 3 days],
It has been found that the antibacterial activity against plant pathogens is excellent 6 For example, Alternaria brassica
e.

Alternaria kikuchiana.

Alternaria 5 alt.

Alternaria 5olani.

Botrytis cinersa+ C1adosporium fulvum.

C1aviceps purpurea.

Cochiobulus mlyabeanus.

Corticiu* rolfsji+Fusariu
m oxyspotum.

Gibberella fujikuroi.

Glog+erella singulata.

Pen1cilli++g+ digitatum.

Phomopsis sp.

Phytophthora capsici+Phyt
ophthora jnfestans+Pjricu
Laria oryzae.

Pythius debaryanu@.

Rh1zoctonia 5olani.

Rhfzoρus chinensisRoselli
nia nec, atr:xSclerotinia
cinerea+5clerotinia sc
lerotiorum+Trichoderma vi
ride.

νalsa ceratosperwa, and Ver.
The growth of plant pathogens such as Licilium dahljae is completely inhibited. In addition, the antibacterial activity against plant pathogenic bacteria was measured using a suspension containing 0.01 to 1% of the fungicidal composition of the present invention (meat extract medium; 30°
For example, Bacillus cereus.

Bacillus 5ubtilis.

Corynebacterium michigane
nse.

pv, s+ichiganense.

Erwinja carotovora+5ubsp,
carotovora pseudos+onas fluorescens+
Pseudomonas glu■aelPseud
owhonas syrtagae pv, lachr
ymans.

Xanthos+onas campstris p
V, pruni, and Xanthomonas ca
It was found that it exhibited favorable antibacterial activity against plant pathogenic bacteria such as M.

Next, a method for producing a fungicidal composition for agricultural and horticultural purposes using silica gel, Ano, and Nomina according to the present invention will be explained.

The sterilizing composition for agriculture and horticulture using silica gel as a matrix according to the present invention can be obtained by chemically treating porous silica gel with an alkaline solution and an aluminate solution.

Examples of alkaline solutions include NaOH, KOH, Li0
A solution of an alkali metal hydroxide such as II is used, and the treatment is carried out by keeping the aqueous phase alkaline, for example at a pH in the range of 9.5 to 11. On the other hand, examples of the latter aluminate solution include NaAZOz and KAfO□.

An alkali metal aluminate solution such as LiAlOT is used, and the chemical treatment of silica gel using the alkali solution and aluminate solution is carried out at room temperature or under heating. Through this chemical treatment, Sing present on the surfaces of the pores and macropores of the silica gel reacts, and an aluminosilicate film containing an ion-exchangeable metal is formed on the active surface of the pores and macropores. Note that the pore volume of the sterilizing composition based on silica gel of the present invention is at least 0.
．． 3d/g and a specific surface area of at least 100nf/g.

A preferred antibacterial agent that accelerates the sterilization rate against mold, etc.
It is also desirable because it exhibits sterilizing power.

The silica gel that has undergone the chemical treatment is washed with water to remove excess alkali and metal components present in the surface phase.

For washing with water, either a batch method or a column method may be applied.Next, ion exchange is performed to retain antibacterial to sterilizing metal ions in the film. That is, the treatment is performed with a neutral or slightly acidic salt solution containing one or more metal ions selected from the group consisting of silver, copper, zinc, and tin as metal ions having a bactericidal effect. Examples of the liquid include AgNOs, Cu(NO3)! ,
Nitrate, Zn
SO4+ 5nSOa+ Cu5Oa-Sulfates like 5nSOa, AgCZO4, Cu((JOa)z, Zn
(Perchlorates such as CIOJz, hydrochlorides such as ZnC1z, organic acid salts such as Ag-acetate, Zn-acetate, Cu-tartrate are used.In addition, one or more of sterilizing metals are used. is ion-exchanged with the ion-exchangeable gold 1i (M in the general formula described below) in the aluminosilicate film at room temperature or under heating to stably stabilize a predetermined amount of sterilizing metal in the film through ionic bonding. A sterilizing composition for agriculture and horticulture using the silica of the present invention is prepared by carrying out the step of supporting the silica. There is no problem even if ions (including metal trace elements) coexist.The replacement rate of the ion-exchangeable metal M in the film and the sterilizing metal depends on the concentration and composition of the salt solution containing the sterilizing metal, and the reaction during ion exchange. It can be adjusted by temperature and time. By adjusting the preparation conditions of the aluminosilicate film and the ion exchange conditions of the bactericidal metal ions, the total amount of bactericidal metal can be adjusted to, for example, 0.003
It is also possible to maintain the concentration at ~0.5 mmol/100 mmol (based on the surface area of the anhydrous disinfectant composition of 100 mmol).

The bactericidal properties of silver, copper, zinc, and tin in the antibacterial to bactericidal aluminosilicate film formed on the active surface of silica gel pores and macropores by adjusting the liquid properties during ion exchange as described above. products based on the hydrolysis of metal ions,
Preventing the tendency for the formed antibacterial film to become contaminated and impure due to the generation of products such as oxides, basic salts, etc., resulting in a decrease in the original antibacterial to bactericidal ability of the bactericidal composition. Is possible.

Instead of ion exchange of the above-mentioned disinfectant metal ion-containing liquid,
Ion exchange may be performed using organic solvents such as alcohols and esters, or using a mixed system of a solvent and water. For example, bactericidal metal ions S that are susceptible to hydrolysis
If an alcoholic solvent such as methyl alcohol or ethyl alcohol is used when replacing n'' by ion exchange with the ion-exchangeable metal M in the film, SnO+ 5n
Since it is possible to prevent Ot + basic tin compounds from being deposited on the film, it is possible to prevent the phenomenon that the antibacterial or sterilizing ability of the film is reduced.Silica gel that has undergone the above chemical treatment is After washing with water until no bactericidal metal ions are observed in the filtrate, the filtrate is dried at 100 to 110° C. to finally prepare a bactericidal composition for agriculture and horticulture using the silica gel of the present invention as a matrix. If it is necessary to further reduce the moisture content depending on the use of the composition, the moisture may be removed by drying under reduced pressure or by increasing the heating temperature to 200' to 350°C.

The total amount of sterilizing metals in the silica gel-based sterilizing composition for agriculture and horticulture prepared as described above exhibits favorable antibacterial to sterilizing power against general bacteria, fungi (molds), plant disease-related teeth, etc. In order to do so, it is preferably at least 0.003 mmol/]0 Orrr, more preferably 0.005 mmol/100 or more [based on the surface area of the anhydrous sterilizing composition of 100 rr], and usually 0
．． The amount may be in the range of 03 to 0.5 mmol/100 rrr.

When two or more bactericidal metals are used in combination, the total amount is preferably within the above range.

Next, a method for preparing a fungicidal composition for agriculture and horticulture using alumina as a matrix according to the present invention will be explained.

The alumina-based bactericidal composition according to the present invention is
It is obtained through a process of chemically treating porous alumina, preferably activated alumina, with an alkaline solution and a silica-containing liquid. Examples of alkaline solutions include NaOH, KO
H, alkali metal hydroxides such as LiOH, Ca
(OR) Alkaline earth metal hydroxides such as t and N
A mixed alkaline solution such as a0H-NazCOs is used to maintain the alumina-containing aqueous phase alkaline, preferably strongly alkaline. On the other hand, examples of the latter silica-containing liquid include sodium metasilicate (Na, SiO).

NazSiOs' 9LO), water glass (e.g. J
IS-1 to 3 products), colloidal silica, silica gel,
Silica-containing liquids such as silica sols and silica hydrosols are used. In addition, the chemical treatment of alumina using the alkaline solution and silica-containing liquid described above is performed under heating up to room temperature.
It is carried out by batch method or column method. Due to this chemical treatment, the Atzas present on the surface of the alumina, i.e., on the pores and macropores, reacts and a film of aluminosilicate containing ion-exchangeable metals is formed on the active surface of said pores. . The alumina that has undergone the chemical treatment described above is washed with water using the bunch method or carlam method, and excess alkali and unreacted substances present in the surface phase are examined. An ion exchange operation is performed.

In this case, the metal ions that have a bactericidal effect include silver,
The treatment is performed using a neutral to slightly acidic solution of salts containing one or more metal ions selected from the group consisting of copper, zinc, and tin. As the liquid, for example, 8 g NO
x, Cu(NO*)x, AgN0s-Zn(NOx
) nitrates like t, Zn5On+ 5nSOa, C
Sulfates such as u5On-3nSOn, 8gc104.
Cu(CJO4)x, perchlorates such as Zn(C!0s)x, chlorides such as ZnC1z, Ag acetates,
Liquids of organic acid salts such as Zn-acetate, Cu-tartrate are used. Using such a saline solution having bactericidal properties, one or more of the bactericidal metals are ion-exchanged with the ion-exchangeable metal M (M in the general formula described below) in the aluminosilicate film at room temperature or under heating. The alumina-based bactericidal composition used in the present invention is prepared by carrying out a step of exchanging the alumina and stably retaining a predetermined amount of bactericidal metal in the film through ionic bonding. A salt containing a bactericidal metal used in the aforementioned ion exchange! ! The ion-exchangeable metal M in the film may coexist with other non-antibacterial metal ions (including metal trace elements) in the solution.
(M in the general formula described below) and the substitution rate of the bactericidal metal depend on the concentration and composition of the salt solution containing the bactericidal metal, the reaction conditions during ion exchange, etc. II! ff can be done. By changing the preparation conditions of the aluminosilicate film and the ion exchange conditions of the bactericidal metal ion to tmm, the total amount of bactericidal metal can be reduced to, for example, 0.0 mm.
0.002 to 0.5 mmol/100 rrf (based on the surface area of the anhydrous sterilizing composition of 100 rrf). By adjusting the liquid properties during ion exchange as described above, the bactericidal properties of silver, copper, zinc, and tin in the antibacterial to bactericidal aluminosilicate film formed on the active surface of the pores and macropores of alumina are improved. The antibacterial film formed by the generation of products such as oxides, basic salts, etc. due to the hydrolysis of metal ions becomes contaminated and impure, resulting in the loss of the original antibacterial properties of the antibacterial composition. It is possible to prevent the tendency for the bactericidal ability to decrease. Instead of the above-mentioned ion exchange of an aqueous solution using a sterilizing metal ion-containing liquid, ion exchange can be carried out using a mechanizing medium such as alcohols or esters, or using a mixed solvent system of solvent and water. For example, when replacing the bactericidal metal ion Sn'' that is susceptible to hydrolysis by ion exchange with the ion-exchangeable metal M in the film, an alcohol solvent such as methyl alcohol or ethyl alcohol or an alcohol-water system may be used. If a mixed solvent is used, it is possible to prevent SnO, SnO□, basic tin compounds, etc. from being deposited on the film, and therefore it is possible to prevent the phenomenon that reduces the bactericidal ability of the film.

Next, the alumina that has undergone the above chemical treatment is washed with water until no sterilizing metal ions are found in the filtrate, and then
The alumina-based agricultural and horticultural fungicidal composition of the present invention is finally prepared by drying at ~110°C.Depending on the use of the composition, it is necessary to further reduce the water content. In such cases, moisture can be removed to the desired level by drying under reduced pressure or by further increasing the heating temperature. In order to exhibit preferable antibacterial to bactericidal power against (molds) and plant disease-related bacteria, the concentration is preferably at least 0.002 mmol/100rrf, more preferably 0.005 mmol/100rrf or more (? (based on the surface area of the bactericidal composition (water) 100 y), and it is usually in the range of 0.002 to 0.5 mmol/100rrf. If two or more bactericidal metals are used, their total amount. is preferably within the above range.

The sterilizing composition for agriculture and horticulture using alumina as a matrix of the present invention should be prepared to have a pore volume of at least 0.4 d1g and a specific surface area of at least 80 nf/g. It is also preferred for promoting the sterilization rate against fungi, plant disease-related bacteria, and the like.

The agricultural and horticultural fungicidal composition containing alumina and silica gel according to the present invention is prepared by the method described above. In preparing these bactericidal compositions, as described above, a non-antibacterial aluminosilicate film is formed on the pores and macropore surfaces of alumina or silica gel, and then the ion-exchangeable material in the film is Ion exchange is carried out with at least one metal ion selected from the group consisting of silver, copper, zinc, and tin that has a bactericidal effect, or at least one metal ion selected from the group consisting of a metal that has a bactericidal effect, W4, and zinc. By performing ion exchange of a solution containing one or more metal ions and tin ions,
An aluminosilicate film with antibacterial to bactericidal properties is formed.

The above-mentioned non-antibacterial aluminosilicate is represented by the following general formula.

x? Jho-AltO,・yS+O,-zH,0 where X and y are coefficients of metal oxide and silicon dioxide, respectively, M is an ion-exchangeable metal, n is the electron valence of M, and 2 represents the number of water molecules. 0M is usually a monovalent metal such as Li, Na, or K, and may also be N114'.
Partial or complete substitution may be made by divalent metals such as Ni, Co or Fe.

The aluminosilicate film mentioned above may be crystalline (zeolite) or amorphous, or both may coexist.The thickness and composition of the aluminosilicate film will depend on the physical properties of the silica gel and alumina raw material, It can be adjusted by the amount used, alkali concentration, amount of aluminate added, reaction temperature, reaction time, etc.

5iOt/AlzOs in both crystalline and amorphous cases
The molar ratio is preferably in the range of 1.4 to 40. Typically S
A type zeolite with iO□/Art's molar ratio of 1.4 to 2.4, X type zeolite with the above ratio of 2 to 3, Y type zeolite with the above ratio of 3 to 6, and SiO□/^! 20. Predominantly amorphous aluminosilicates with a molar ratio of from 1.4 to 30 or mixtures of the crystalline and amorphous aluminosilicates mentioned above are used. The film made of the non-antibacterial aluminosilicate is made antibacterial or sterilized by the ion exchange method described above.

In the agricultural and horticultural fungicidal composition containing silica gel or alumina as a matrix of the present invention, the matrix may contain metal elements necessary for plant growth in the antibacterial or bactericidal coating or both.

As the metal element, at least one metal selected from the group consisting of potassium, calcium, molybdenum, magnesium, zinc, manganese, titanium, cobalt, nickel, copper, and iron is used.

These metal elements may be stably immobilized using ion exchange technology into the film containing the silica gel or alumina-based germicidal composition used herein.

Alternatively, salts containing the above-mentioned metal elements can be simply mixed and adhered to the sterilizing composition for use. Adopting such a method has the advantage of not only providing antibacterial or bactericidal effects, but also promoting the growth of plants, etc.

The substance of the present invention is suitable for use as a fungicidal composition for agricultural and horticultural purposes such as fields, paddy fields, orchards, tea plantations, pastures, and lawns (e.g. golf courses), has little phytotoxicity, and is resistant to various diseases. be effective. Furthermore, it is of course possible to use Reijing in combination with other agricultural and horticultural fungicides, insecticides, herbicides, growth regulators for plants, etc., fertilizers, and the like.

In the specific use of the agricultural and horticultural fungicidal composition of the present invention, the shape of the composition may be powder, granules, or other shapes (spherical, pellet, etc.), but there are no restrictions on the shape. No, the powder can be used as is without adding any other ingredients. In addition, other ingredients may be added to the main ingredient and used, and as mentioned above, the fungicidal composition of the present invention can also be used by adding metal elements necessary for plant growth to the main ingredient. Zeolite, kaolin, clay (acid clay, activated clay), which are commonly found in drug use,
Solid carriers such as bentonite, talc, diatomaceous earth, liquids such as water, surfactants used for emulsifying and dispersing purposes such as alkyl sulfate salts, dialkyl sulfosuccinates, various metal soaps, alginates, CMC(
It can also be used by mixing it with formulation auxiliaries such as carboxymethyl cellulose (carboxymethylcellulose) to formulate granules, wettable powders, powders, suspensions, etc.

Next, examples of methods for applying the fungicide composition III of the present application include foliage spraying, soil treatment, seed disinfection, and others, but any application method commonly used by those skilled in the art can be used. can.

The agricultural and horticultural fungicide according to the present invention targets a wide range of diseases, such as late blight (potato blight), black spot of pears,
Tomato late blight (ring spot, spot), potato late blight, cucumber late blight (downy mildew, tanzo), sesame leaf blight, grape late blight, strawberry late blight (gray mold), vegetable soft rot, black rot Powder formulations exhibit favorable effects against diseases and the like.

■ The size of the pores (cyclobore) of the agricultural and horticultural fungicidal composition containing silica gel and alumina of the present application is as follows:
Since it is larger than known aluminosilicate-based (zeolite) disinfectants, the dissociated germicidal metal ions of this composition diffuse through the pores, making it easier for the container to come into contact with pathogenic fungi. Become. On the other hand, in the case of known bactericidal compositions based on aluminosilicate, such as antibacterial zeolite, the pore size is small, so it takes time for dissociated bactericidal metal ions to diffuse, and in some cases, fungi and In some cases, contact with others was impossible. Therefore, even if porous aluminosilicate (zeolite) particles are used to increase the apparent specific surface area, the area where bacteria can come into contact with the sterilizing metal will not increase significantly, and antibacterial or bactericidal performance is expected. It did not increase as much as it did. In other words, even if the sterilizing metal was present on the surface of the matrix, there was a dead space where it could not come into contact with the bacteria.

This is not the case with the agricultural and horticultural germicidal composition of the present invention, which uses silica gel or alumina as a matrix, and all the sterilizing metals present on the surface of the matrix can come into contact with bacteria and act effectively.

Furthermore, in the present invention, the base silica gel and alumina are coated with an antibacterial layer of aluminosilicate substituted with a sterilizing metal, so the amount of wasted sterilizing metal that exists inside and does not come into contact with bacteria is reduced. It decreased drastically.

Due to the above two factors, the effective utilization rate of the sterilizing metal in the sterilizing composition for agriculture and horticulture of the present invention, that is, the ratio of the metal present on the surface to the metal used, is significantly improved.
Since excellent antibacterial or sterilizing performance can be obtained with a small amount of use, this principle is extremely effective as a fungicide for agriculture and horticulture.

Next, examples of the present invention will be described, but the present invention is not limited to the examples.

Disaster Management Team 2 This example relates to a preparation example of the disinfectant composition for agriculture and horticulture of the present invention, which uses silica gel as a matrix and combines silver and zinc as disinfectant metals.

Silica gel [Toyoda's spherical silica gel (specific surface area, 45
(lITf/g; pore diameter, 60A, pore volume, 0.
75d/gi particle size, 40wesh bath)] Approx. 1.3
2.52 kg of demineralized water was added, and the mixture was then stirred at 400-450 rpm to form a homogeneous slurry. To this, 0.5N sodium hydroxide solution was gradually added until the pH of the slurry liquid was adjusted to 9.
It was adjusted to be 5-10.0. 0.27 mol/! for the above slurry liquid! After an aqueous solution of sodium aluminate with a concentration of about 2.61 is added, the slurry liquid has a concentration of about 2.61
The mixture was stirred at 450 to 500 rpm for about 15 hours at 0' to 23°C to form a film of aluminosilicate on the pore surface of the silica gel.Then, filtration was performed, and the obtained solid phase was washed with water. Excess alkali and unreacted sodium aluminate present in the solid phase were removed. In this case, the pi of the filtrate during water washing was maintained at about 9.

AgNO3-Zn was added to the solid phase that had been washed with water.
(NOx) 2 mixed liquids (AgNO, and Zn CN0
x) Water dilutions containing 0.6M and 0.2M as z, respectively, pH=4.1) were added and the resulting mixture was kept at 20° to 21”C and heated to about 15 Continuous stirring was carried out at 450-500 rpm for an hour.By carrying out the above ion exchange reaction, an antibacterial composition containing bactericidal silver and zinc was prepared, which was then filtered and washed with water. Excess silver and zinc present in the surface phase were removed.The washed product was dried at 100° to 110°C to prepare a germicidal composition for agriculture and horticulture, which uses the silica gel of the present invention as a matrix and contains silver and zinc as germicidal metals. things were prepared.

Specific surface area of the bactericidal composition prototyped in Example-1
Lt[ due to arrival of 9rtr/g (BET Nt gas 11)
), the pore volume is 0.67cj/g, and the quantitative values of silver and zinc are 3.79% and 0.6%, respectively.
The amounts of silver and zinc per 100 μm of surface area of the fungicidal composition obtained in Example-1 (anhydrous basis) were 0.11 mmol and 0.04 mmol, respectively. .

Table 1 Double Plate 21 Nisou (Example 1) Ag Zn 319 0.11 0.04 This example shows the antibacterial effects of a silica gel-based agricultural and horticultural fungicidal composition against plant pathogenic bacteria and plant pathogenic bacteria. This relates to gender evaluation tests. As a fungicidal composition for agricultural and horticultural use, a fungicidal composition based on silica gel in which silver and zinc are combined as bactericidal metals (Example-1; Ag=0
．． 11 mmol/100n (; Zr+ = 0.04 mmol/100rrf, specific surface area 319 ho/g; pore volume 0.67 cj/g) is used, and the evaluation method for its antibacterial activity is M-drug experimental method Vol. It was carried out according to the antibacterial activity measurement method of (Soft Science).

In this test, PDA (Po
Agar) medium was used, and a meat extract medium was used for plant pathogenic bacteria. The growth state of the bacteria was evaluated by culturing at 25°C for 3 days in the former medium and at 30°C in the latter medium for 3 days. The evaluation symbols are 0 (all (no bacterial growth), 1 (bacterial growth on less than 10% of the total surface area)
, 2 (growth of bacteria on less than 30% of the total surface area), 3 (growth of bacteria on less than 60% of the total surface area), and 4 (growth of bacteria on less than 60% of the total surface area)
A four-stage symbol was used: (bacterial growth of % or more).

The test results are shown in Table-2. When evaluating antibacterial activity, the above-mentioned agricultural and horticultural bactericidal composition was added to the culture medium and a solution containing 0.08% and 0.5% (
suspension).

The indicated 0% is a blank test liquid, which does not contain the above-mentioned bactericide. The main rules for using silica gel as a host are Alternaria kikuchiana (black spot on pears), Alternaria 5olani () blight on pears: ring spot disease; summer wasting disease on potatoes), Phytoph
thora capsici (cucumber blight),
It has shown favorable effects against plant pathogens such as Pythius debaryanu++ (soybean disease).

Also Xantho+*onas campestris
pv, pruni (black rot), χanthoyaon
as campestrrs pv, oryzae (
It is also highly effective against plant pathogenic bacteria such as seed leaf blight).

Table 2 Antibacterial activity test (Example 2) This example relates to an evaluation test of antibacterial activity against plant pathogenic bacteria and plant pathogenic bacteria of an agricultural and horticultural fungicidal composition containing activated alumina as a matrix.

A fungicidal composition for agriculture and horticulture is a fungicidal composition containing activated alumina, which is a composite of silver and copper as a bactericidal metal (Ag=0.14 mmol/100 rrr).

Cu=0.06 mmol/100nf, specific surface area 20
A fine powder of 3rrf/g; pore volume 0.63cj/g) was used, and the evaluation method and criteria for its antibacterial activity were as follows:
This drug, which is exactly the same as in Example-2, was added to the medium,
As in Example-2, the concentrations were maintained at 0.08% and 0.5% liquids (suspensions).

Table-3 Antibacterial activity test (Example-3) 0.5χ 0.08χ 0χ Piricularia oryzaeXanthom
onas caspestris pv, prun
io 1 4 The test results are shown in Table 3, but the main rule that activated alumina is Cochiobolus mlyabean
us (sesame leaf blight), Glomerella ci
ngulata (grape rot), Pirfcul
It shows favorable antibacterial activity against plant pathogenic bacteria such as Aria oryzae (rice blast disease). Also Er
winja carotovora 5ubsp, ca
rotovora (vegetable soft rot), Xanthom
onas cowpestris pv.

It also exhibits favorable effects against plant pathogenic bacteria such as P. pruni (black rot).

This example relates to a tomato late blight control test using a fungicidal composition for agricultural and horticultural use containing activated alumina as a matrix.

In this test, a bactericidal composition (^g=0.14 mmol/10 g = 0.14 mmol/10
0rrf; Cu=0.06 mmol/100nf
, specific surface area 203ITr/g; pore volume 0.63d/
g) fine powder was used.

A homogenized wettable powder was obtained by pulverizing a mixture consisting of 92 parts of the above-mentioned fungicidal composition, 5 parts of calcium lignin sulfonate, and 3 parts of sodium lauryl sulfate. A certain amount of this was collected and diluted with water to prepare solutions containing 0.12% and 0.51% fungicidal compositions for agricultural and horticultural use.

These liquids were used to control and test tomato late blight.

Soil containing fertilizer was placed in a plastic flower pot, tomatoes were sown, and grown for 22 days. Stalk and foliage spraying was carried out on tomato seedlings that had developed their second and third true leaves, taking care to ensure that the chemical solution prepared by the above-mentioned method was sufficiently attached to the leaf surface. After spraying, Phytophthora bacillus (Alternaria)
Tomatoes were inoculated by spraying with a spore suspension of 5 olani). After inoculation, growth continues for another week and leaves,
The degree of disease on the stems was observed and the control effect was determined.

The agricultural and horticultural killing composition of the present invention was mixed with o, 12% and 0
．． When the solution containing 51% was sprayed on tomato seedlings, it exhibited an excellent control effect, and no disease was observed on the leaves and stems of tomato plants. The evaluation value of control efficacy was 5 when using either chemical solution. However, if the disease state of the test tomatoes is observed and there are no bacterial flora or lesions on the leaves, stems, etc., the evaluation value will be 5.
If it is observed in about 10%, it is 4. If it is observed in about 30%, it is about 3. If it is observed in about 50%, it is 2. If it is observed in 70%, it is rated as 1, and the difference from the disease onset state when no drug solution is used. If this was not observed, the control efficacy was set to 0.

Claims (1)

[Scope of Claims] 1. The matrix is at least one inorganic substance selected from the group consisting of silica gel and alumina, and the matrix has an antibacterial or bactericidal film of aluminosilicate that retains metal ions having a bactericidal effect on the surface of the matrix. A bactericidal composition for agriculture and horticulture, characterized by comprising: 2. In the matrix, at least one metal selected from the group consisting of potassium, calcium, molybdenum, magnesium, zinc, manganese, titanium, cobalt, nickel, copper and iron is added to the antibacterial or bactericidal film or both. The fungicidal composition for agricultural and horticultural use according to claim 1, characterized in that it contains a fungicide. 3. The fungicidal composition for agriculture and horticulture according to claim 1 or 2, wherein the antibacterial or bactericidal film is crystalline and/or amorphous. 4. Claims 1 to 3, wherein the antibacterial or bactericidal film contains at least one metal ion selected from the group consisting of silver, copper, zinc, and tin as a metal ion having a bactericidal effect. The fungicidal composition for agriculture and horticulture according to any one of the above. 5. The total amount of metal ions having a bactericidal effect is 100 m^2 on the surface area of the bactericidal composition based on anhydrous silica gel.
The fungicidal composition for agricultural and horticultural use according to any one of claims 1 to 4, characterized in that the fungicidal composition is present in an amount of at least 0.003 mmol per liter. 6. The total amount of metals and ions having a bactericidal effect is 100 m^2 on the surface area of a bactericidal composition based on anhydrous alumina.
The fungicidal composition for agricultural and horticultural use according to any one of claims 1 to 5, characterized in that it is present in an amount of at least 0.002 mmol per unit. 7. An aluminosilicate whose plant, plant part, or native habitat and matrix of the plant is at least one inorganic substance selected from the group consisting of silica gel and alumina, and which retains metal ions having a bactericidal action on the surface of the matrix. A method for protecting plants from fungal diseases, which comprises contacting plants with a fungicidal composition for agricultural and horticultural use, which is characterized by having an antibacterial or bactericidal film.