JPH01156905A - Fungicide for agricultural and horticultural use - Google Patents

Abstract

PURPOSE:To obtain the title fungicide effective against plant blights in plowed land, paddy field, orchard, etc., by using a crystalline zeolite selected from faujasite group, shabasite group and phillipsite group as an active component. CONSTITUTION:The objective agent contains one or more kinds of crystalline zeolite selected from faujasite group, shabasite group and phillipsite group and expressed by formula I (M is Na or K; 0<a<=1, 3<b<=12, 0<=c<=20) as an active component. Especially excellent controlling effect can be attained by the use of a crystalline zeolite selected from faujasite group and phillipsite group and expressed by formula II (0<a<=1, 3.5<b'<8, 0<=c<=20). It can be applied to a field by arbitrary method and the preferable rate of application is usually 0.3-300g per 1 are.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides one or more crystals selected from the group consisting of the faujasite group, the chabasite group, and the phillipsite group represented by the following general formula CI]. zeolite (hereinafter referred to as
It is called the substance of the present invention. ) as an active ingredient.

acuo-(1-a)M2O-A120. -bsio2
-cH20[I]c where M is a sodium atom and/or
or represents a potassium atom, and a, b and C each represent a numerical value within the following range.

O<a≦i, a<bS12゛, O≦C≦20) <Prior art> Conventionally, inorganic copper agents such as Bordeaux liquid have been used in fields such as fruit trees and vegetable crops.

However, these known fungicides are not necessarily satisfactory, as they are effective against a narrow range of diseases and have limitations in their applicability, such as causing phytotoxicity to crops. The development of high-performance drugs that are effective at low doses is eagerly awaited.

Under these circumstances, the inventors of the present invention have conducted intensive studies to find a drug that is safe for crops and has excellent activity against various diseases of fruit trees, canola, etc., and surprisingly, the above-mentioned book was discovered. The inventors discovered that the invented substance has extremely excellent bactericidal activity and does not cause any problematic chemical damage, leading to the present invention.

Until now, Japanese Patent Publication No. 164 has described that an aluminosilicate obtained by ion-exchanging copper ions can be used as a fungicide for agricultural and horticultural purposes.

<Problem to be solved by the invention> However, the copper-containing aluminosilicate described in the above literature does not actually have strong bactericidal activity per copper, and cannot necessarily be said to compensate for the drawbacks of conventional inorganic copper agents. hard.

Means for Solving the Problems> As a result of intensive study by the present inventors on the development of a drug that has high bactericidal activity per copper and therefore exhibits a sufficient effect with a low dose of copper, the present inventors found that the general formula It was discovered that the crystalline zeolite represented by α] has extremely high activity per copper.

Comparing the activity per copper with existing inorganic copper agents, it was found that the substance of the present invention was more than 10 times more active against many diseases as described in the Examples, although it differs depending on the target disease. This marked improvement in the activity per copper is epoch-making, and although copper fungicides have been researched for over 100 years, highly active copper fungicides such as the one of the present invention have not yet been developed. It had not been discovered.

A significant increase in activity per copper provides various advantages in crop disease control.

That is, since the agricultural and horticultural fungicide of the present invention is highly effective against various plant diseases, it is possible to reduce the amount of chemicals used, and therefore, the phytotoxicity of the crops to which it is applied can be significantly improved, and it is It has the great advantage of being fully applicable to crop fields where it has been difficult to use existing metal-containing fungicides.

Furthermore, since the activity per copper has been greatly improved, it has the advantage that it can be used without increasing the amount of residual copper in areas where copper residue in the soil is significant.

Among the substances of the present invention, those that are particularly excellent in terms of their pesticidal efficacy are one or more crystalline zeolites selected from the group consisting of the faujasite group and the phillipsite group represented by the following general formula (9). It is.

acuO-(1-a)M2O-AlzO3-bsi02
-cH20ol) [wherein M is a sodium atom and/or
or represents a potassium atom, and a, b' and C each represent a numerical value within the following range.

0<a≦1, s, 5<b<8.0≦C≦20] The content of copper in the substance of the present invention can be arbitrarily determined, but preferably, M2 in the general formula is replaced with a copper atom. As much as possible.

The substance of the present invention can be synthesized hydrothermally by a known method, for example, by mixing an aqueous solution of sodium aluminate or potassium aluminate with an aqueous solution of sodium silicate or potassium silicate at a predetermined concentration ratio in an aqueous caustic soda solution or an aqueous caustic acid solution. Zeolite, which is a precursor of the substance of the present invention, is produced by the following method, and then these zeolites and a water-soluble copper salt are subjected to an ion exchange reaction in water or alcohol. As the water-soluble copper salt used in the reaction, for example, mineral acid salts such as cupric chloride, cupric sulfate, cupric nitrate, etc. are preferable. Organic acid salts such as cupric acetate and cupric formate, or ammonia copper complex salts can also be used.

Since the substance of the present invention exhibits excellent effects against plant diseases, it can be used for various purposes as an active ingredient in agricultural and horticultural fungicides.

Plant diseases that can be controlled by the substance of the present invention include the following diseases.

Soft rot of various vegetables (Erwinia carotovo)
ra), solanaceae bacterial wilt (Pseudomonas
solanacearum), bacterial spot bacterial disease of cucumber (
Pseudomonas syring
ae pv.

maculicola), black rot (Xanthomo
nas campest-ris), tumefaciens disease (
Agrobacterium tumefaciens
), tomato canker disease (Corynebac-teri
um michigananense), bacterial rice blight (Pseudomonas glumae), tobacco wildfire disease (Pseudomonas tabaci)
), citrus canker disease (Xanthomonas ca
mpestris pv, citri), rice leaf blight (Xanthomonas oryzae), and downy mildew of Japanese vegetables and radish (Peronospora b).
rassicae), spinach downy mildew (Pero
nospora 5pinaciae), tobacco downy mildew (Peronospora tabacina),
Cucumber downy mildew (Pseudoperonospor)
a cubensis), downy mildew of grapes (Plas
mopara viticola), downy mildew of umbelliferous plants (Plasmopara n1vea), late blight of apples, strawberries, and ginseng (Phytoph
th-ora cactorum), gray late blight (Phytophthora capsi) of tomatoes and cucumbers
ci), pineapple blight (Phytophth)
oracinnamomi), potatoes, tomatoes,
Phytophtora 1nfesta
ns), late blight of tobacco, field beans, and green onions (Phytop
hthoranicotianae Var, n1c
otianae), spinach damping-off (Pythi
um sp, ), cucumber seedling damping-off (Pythium sp.
aphanidermatum), Pythium sp., tobacco seedling damping-off (Pythium debaryanum), Pythium rot (Pythium aphane), Pythium sp.
idermatum, P. debaryanum.

P, irregulare, P, myrio
tylum, P. ultimam), rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus mlyabeanus)
), apple scab (Venturia 1naeq)
ualis), rot disease (Valsa mali),
leaf spot disease (Alternaria mali), black spot disease of pear (Alternaria kikuchian)
a), Venturia nashicol
a), citrus black spot (Diaporthe ci)
tri), oyster anthracnose (Gloeosp-orium
kaki), deciduous disease (Cercospora ka
Ki.

Mycosphaerella nawae), late rot of grapes (tritici), late rot of grapes (Leptos tritici),
phaeria nodorum), anthracnose of cucurbits (
Colletotrichum lagenarium
), vine blight (Mycosphaerella mel
onis), tomato ring spot disease (Alternaria
5olani), Tahakono Akaboshi disease (Alterna
ria longipes), anthracnose (Collet
otrichum tabacum), sugar beet brown spot (Cercospora beticola),
Potato summer sky disease (Alternaria 5ola)
ni), groundnut brown spot (Cercospora
arachidicola), diver's brown spot (5
eptoria glycines), black spot disease (D
i apor thephaseolol, um),
Anthracnose (Col letotrichum sp.),
Examples include Cercospora kikuchii.

The substance of the present invention can be used as an agricultural and horticultural fungicide in fields, paddy fields, orchards, tea plantations, pastures, lawns, etc., and can also be used in other agricultural and horticultural fungicides, insecticides, acaricides, and fericides. It can also be used in combination with insecticides, herbicides, plant growth regulators, and fertilizers.

When the substance of the present invention is used as an active ingredient of a disinfectant, it may be used as it is without adding any other ingredients, but it is usually combined with a solid carrier, liquid carrier, surfactant, or other formulation auxiliary. They are mixed and used in formulations such as granules, wettable powders, suspensions, and powders. The content of the substance of the present invention in the preparation is 0.1 to
99.9%, preferably 1-99%.

The above-mentioned solid carriers include fine particles such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Powders or granules may be mentioned, and liquid carriers may include water.

Surfactants used for emulsification, dispersion, wet layer, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan Examples include nonionic surfactants such as fatty acid esters and polyoxyethylene sorbitan fatty acid esters.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isopropyl acid phosphate), and the like.

In addition, examples of methods for applying the agricultural and horticultural fungicide of the present invention include foliage spraying, soil treatment, seed disinfection, etc.
Any application method commonly used by those skilled in the art can be used.

When the substance of the present invention is used as an active ingredient of a fungicide for agriculture and horticulture, the application amount of the active ingredient depends on the target crop, target disease, degree of disease occurrence, formulation form, application method, application timing, weather conditions, copper content, etc. Although it varies depending on the amount etc., it is usually 0.8 to 600 g per are, preferably 0.3 to 300 g, and when applying a wetting agent, suspending agent, etc. diluted with water, the application concentration is 0. .015-1.5%, preferably 0.015% to 1.5%, preferably 0.015% to 1.5%, preferably 0.
03 to 0.6%, and powders, granules, etc. are applied as they are without any dilution.

Since the agricultural and horticultural fungicide of the present invention is highly effective against various plant diseases, it has the great advantage of being able to reduce the amount of chemicals used, and therefore being fully applicable to the crops to which it is applied. .

<Effects of the Invention> The agricultural and horticultural fungicide of the present invention has excellent effects in that it is highly effective against plant diseases caused by various plant pathogenic bacteria and does not cause any problematic phytotoxicity.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

First, a formulation example will be shown. Note that parts represent parts by weight.

Formulation Example 1 A wettable powder is obtained by thoroughly pulverizing and mixing 50 parts of the substance of the present invention, 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide.

Formulation Example 2 A wettable powder is obtained by thoroughly pulverizing and mixing 95 parts of the substance of the present invention, 3 parts of calcium lignosulfonate, and 2 parts of sodium lauryl sulfate.

Formulation Example 3 50 parts of the substance of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 44 parts of water were mixed,
A suspension is obtained by wet milling until the particle size of the active ingredient is less than 5 microns.

Formulation Example 4 5 parts of the substance of the present invention, 85 parts of kaolin clay, and 1 part of talc
A powder is obtained by thoroughly grinding and mixing 0 parts.

Formulation Example 5 20 parts of the substance of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 48 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, followed by granulation and drying. Granules are thereby obtained.

Next, test examples demonstrate that the substance of the present invention is useful as a fungicide for agriculture and horticulture.

In addition, in this test, the test substance was prepared by the operation shown below.

Na, 026.3% by weight, A40348.2% by weight and H
Sodium aluminate 15 containing 2O30.5% by weight
Sodium hydroxide 68 containing f and Na2O77.5% by weight
．． 85y was dissolved in distilled water 27.6.04f.

This solution was added with stirring to 852.43 g of an aqueous colloidal silica sol containing 0.4% by weight of Na2O and 0.5% by weight of 5i02. The substance obtained here is 13.9
Na20-A$203-28.2SiO□・470.9
It is indicated by H20.

The reactor was then sealed and heated to 100 °C for 24 h at room temperature.
The mixture was stirred at C for 24 hours. Next, the precipitated powder crystals are dried in an oven under reduced pressure, and then the crystals are washed until the pH of the washing liquid is about 8 to 8.
It was washed with distilled water until the temperature reached 9 and dried at 120°C for 16 hours.

Next, 118 g of 0.04 M copper sulfate aqueous solution was added to this crystal 5y.
After adding +/, the pH in the system was adjusted to 4.0 using 10% sulfuric acid.
2 and stirred at 70°C for 4 hours to perform an ion exchange reaction. After the ion exchange reaction was completed, the reaction solution was filtered, and the obtained crystals were washed with distilled water until copper ions and sulfate groups were no longer detected, and then dried at 120°C for 16 hours.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the faujasite group. Also, elemental analysis showed that the Si/A/atomic ratio was 2.68 and the copper content was 4.6% by weight, and the substance was 0,48 CuO-0,52Na20・A/203-5
．． It is represented by 36SiO2.9.25H20.

Na2O2 6 parts wt%, A72034&2 wt% and H2
Sodium aluminate 25f containing O30.5% by weight
Sodium hydroxide containing 77.5% by weight of Na2O and 52.
41 was dissolved in distilled water 612.11. Cono solution with N
It was added with stirring to 379.91 ml of an aqueous solution of sodium silicate containing 9.2% by weight of a2O and 29.0% by weight of 5iO2. The substance obtained here is 12.5Na20-A12
03・t7. It is designated as 1o2-454.5H20.

The reactor was then sealed and stirred at 100°C for 48 hours.

The precipitated powder crystals were then dried under reduced pressure, washed with distilled water until the pH of the washing solution became about 8-9, and dried at 120°C for 16 hours.

Next, copper ion exchange was performed in the same manner as the method for preparing the substance (1) of the present invention.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the phillipsite group. Further, elemental analysis revealed that the Si/A5 atomic ratio was 1.91 and the copper content was 3.8% by weight. As a result of electron microscopy measurement, the average particle diameter was 2.0 μm, and the substance was 0.32 Cu0 ・0.68 Na20 ・A
It is represented by 12O3.3.82SiOz.7.79H20.

Inventive product 1 (3) Distilling 15 da of sodium aluminate containing 6.3% by weight of Na20, 343.2% by weight of AA'zO and 0.5% by weight of H2O and 65.74f of sodium hydroxide containing 77.5% by weight of Na2O. Dissolved in 519.09f of water.

5102 (Aerosil) 107.49 Da was added to this solution with stirring. The substance obtained here is 18.9
NazO・A(bos・28.2SiO+・470,
It is indicated by 9H20.

The reactor was then sealed and kept at room temperature for 24 hours.
Stirred at ℃ for 24 hours. Next, the precipitated powder crystals are dried under reduced pressure, and then the crystals are washed until the pH of the washing solution is about 8 to 8.
It was washed with distilled water until the temperature reached 9 and dried at 120''C for 16 hours.

Next, copper ion exchange was performed in the same manner as in the preparation method for the substance (1) of the present invention.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the phillipsite group. Elemental analysis revealed that the Si/A4 atomic ratio was 2.89, the copper content was 3.2% by weight, and the substance was 0.32CuO-0,68Na20-A/203.4-
785i02 ・9.48 Shown as H2O.

Substance of the present invention (4) Na20 26.8% by weight, A11034.32% by weight
and 0.5% by weight of H2O3. This solution was mixed with Na2O0.4% by weight, 5iO230,
Aqueous colloidal silica sol 852.4Bf containing 5% by weight
was added to the solution while stirring. The substance obtained here is l 3
．． 9Na2o @ A, g203・28.23102
- It is indicated by 470.9H20.

The reactor was then sealed and heated to 100 °C for 24 h at room temperature.
After stirring at 100° C. for 24 hours, the mixture was returned to room temperature and stirred again at 100° C. for 48 hours.

Next, the precipitated powder crystals were dried under reduced pressure, and then washed with distilled water until the pH of the washing solution became approximately 8 to 9, and dry ion exchange was performed at 120°C for 16 hours. .

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the phillipsite group. According to elemental analysis, the Si/Al atomic ratio is 2.59, the copper content is 3.4% by weight, and the material is 0.35CuO-0,65Na20-Ad203-5.
It is shown as 18SiO2°9.79H20.

Sodium aluminate 1 containing 26.3% by weight of Na2O, 343.2% by weight of Alρ and 5% by weight of H2OBo
Sodium hydroxide 6 containing 5f and Na2O77.5% by weight
3.851 was dissolved in distilled water 276.049. Kono solution is Na2O6, 4% by weight, 5iO230, 5% by weight
was added with stirring to an aqueous colloidal silica sol 352.43F containing. The substance obtained here is 18.9 Na2”” Al1203・28.2 S
102 470.9 H2O.

The reactor was then sealed and heated to 100 °C for 24 h at room temperature.
Stirred at C for 18 hours. Next, the precipitated powdery crystals are collected under reduced pressure, and then the crystals are collected until the pH of the washing solution is about 8-8.
It was washed with distilled water until the temperature reached 9 and dried at 120°C for 16 hours.

Next, copper ion exchange was performed in the same manner as in the preparation method for the substance (1) of the present invention.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the faujasite group. Further, elemental analysis revealed that the Si/Al atomic ratio was 2.58 and the content/amount of copper was 4.7% by weight.
16Si02-8.93H20.

Substance of the present invention (6) Na20 26.3% by weight, A120348.2% by weight
Sodium aluminate 151 containing 7.5% by weight of Na2O and 141.63F sodium hydroxide containing 77.5% by weight of Na2O were dissolved in 68.09f of distilled water. This solution was added with stirring to an aqueous colloidal silica sol 128.7:af containing 0.4% by weight of Na2O and 30.5% by weight of 5iO2. The substance obtained here is designated as 29-ONazO.A12034e.

The reactor was then sealed and heated to 100 °C for 24 h at room temperature.
The mixture was stirred at C for 130 hours. Next, the precipitated powder crystals were collected under reduced pressure, and then the crystals were collected until the pH of the washing solution was about 8.
Washed with distilled water until ˜9 and dried at 120″C for 16 hours.

Next, copper ion exchange was performed in the same manner as in the preparation method for the substance (1) of the present invention.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a cohesive zeolite belonging to the faujasite group. Also, elemental analysis shows that the Si/A/atomic ratio is 2.76 and the copper content is 5.4% by weight, and the substance is 0.57 CuO-0,43Na20-A#2035
．． 52S io2'-8,87H20.

Na2O26J wt%, A4034 B, 2 wt% and H
Sodium aluminate 15 containing 2O80.5% by weight
Sodium hydroxide containing 77.5% by weight of Na2O63
．． 85f was dissolved in 276.04f of distilled water. This solution was mixed with 200.4% by weight of Na and 30.5% by weight of SiO□.
was added with stirring to an aqueous colloidal silica sol 852.48f containing. The substance obtained here is 13.9Na20-A1203" 28.25i02-
470.9H20.

The reactor was then sealed and kept at room temperature for 24 hours and then at 100°C.
The mixture was stirred for 65 hours. Next, the precipitated powdery crystals were collected under reduced pressure, and the crystals were collected until the pH of the washing solution was about 8 to 9.
The sample was washed with distilled water until dry and dried at 120°C for 16 hours.

Next, copper ion exchange was performed in the same manner as in the preparation method for the substance (1) of the present invention.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the faujasite group. Further, elemental analysis revealed that the Si/Ad atomic ratio was 2.35 and the copper content was 5.1% by weight. Further, as a result of electron microscopy measurement, the average particle diameter was 1.0 μm, and the substance was 0.48CuO-0,52Na20-A1
203-4.705i02-8.15H20.

Crystalline zeolite before copper ion exchange was obtained in the same manner as the method for preparing the substance (5) of the present invention. Next, 0.3M copper sulfate aqueous solution 2070 was added to the zeolite 901 obtained in this way.
After adding yet, the pH in the system was adjusted to 4 using 10% sulfuric acid.
．． 2 and stirred at 70° C. for 4 hours to perform an ion exchange reaction. After the ion exchange reaction was completed, the reaction solution was filtered, and the obtained crystals were washed with distilled water until copper ions and sulfate groups were no longer detected, and then dried at 120° C. for 16 hours.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the faujasite group. Further, elemental analysis revealed that the Si/A7 atomic ratio was 2.58 and the copper content was 7.8% by weight. Further, as a result of measurement using an electron microscope, the average particle diameter was 1.5 μm, and the substance was 0.78CuO-0,22Na20-A1203-5.
163iO2-8,09H20.

Substance of the present invention (9) Naρ26.3% by weight, Alp343.2% by weight and H2
Sodium aluminate 15f containing O30.5% by weight
and sodium hydroxide containing 77.5% by weight of Na2O63.
85f was dissolved in 276.041 g of distilled water.

The Kono solution was added with stirring to an aqueous colloidal silica sol 352.43F containing 0.4% by weight of Na2O and 0.5% by weight of 5i02. The material obtained here is 13.9 N
a2O・A1203-28.281o2-470.9H
,0.

The reactor was then sealed and kept at room temperature for 24 hours and then at −80 °C.
Stirred at C/6g for 6 hours. Next, the precipitated powder crystals were collected under reduced pressure, and then the crystals were collected until the pH of the washing solution was about 8.
It was washed with distilled water until the temperature reached ~9 and dried at 120°C for 16 hours.

Next, add 100 ml of 0.048 M copper sulfate aqueous solution to 5 d of this crystal.
ml, the pH of the system was adjusted to 4.0 ml using 10% hydrochloric acid.
2 and stirred at 75°C for 4 hours to perform an ion exchange reaction. After the ion exchange reaction was completed, the reaction solution was filtered, and the obtained crystals were washed with distilled water until copper ions and sulfate groups were no longer detected, and then dried at 120° C. for 16 hours.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the faujasite group. Further, elemental analysis revealed that the Si/A1 atomic ratio was -2.47 and the copper content was 7.0% by weight. Further, as a result of electron microscopy measurement, the average particle diameter was 0.5 μm, and the substance was 0.68CuO-0, a2Na20-A
/203・4.94SiO2・8.02HzO.

Substance of the present invention (10) 15f of sodium aluminate containing 26.8% by weight of Na20, 43.2% by weight of A6zOa and 30.5% by weight of HzO and 20.89d of sodium hydroxide containing 77.5% by weight of Na2O. 89.71 g of potassium hydroxide containing .0% by weight was dissolved in distilled water 266.42F. This solution was mixed with Na20 0.4% by weight SiO□30.
Aqueous colloidal silica sol 354.53F containing 5% by weight
was added to the solution while stirring. The six substances obtained here are 5,6 and 20.5.5Na20-A1203.28.5SiO2
- Indicated by 463H20.

The reactor was then sealed and kept at room temperature for 24 hours.
The mixture was stirred for 70 hours at c. Next, the precipitated powder crystals are dried in an oven under reduced pressure, and then the crystals are washed until the pH of the washing liquid is about 8 to 8.
It was washed with distilled water until the temperature reached 9 and dried at 120°C for 16 hours.

Next, copper ion exchange was performed in the same manner as in the preparation method for the substance (1) of the present invention.

The powdery substance thus obtained was confirmed to be a crystalline zeolite belonging to the chabasite group by X-ray diffraction. Further, elemental analysis revealed that the Si/Al atomic ratio was 3.11, the copper content was 1.7% by weight, and the material was composed of 0.21CuO-0,35 and 20-0.44Na20-
A/203-6.22SiO2.12.53H20.

Sodium aluminate 15f containing 6.8% by weight of Na2O2, 2% by weight of A&Os 4B and 0.5% by weight of H2O, sodium hydroxide 2B, 58f containing 77.5% by weight of Na2O, and water containing 2084.0% by weight. 14.25 g of potassium oxide was dissolved in 179.959 g of distilled water. This solution was mixed with Na2Oo, 11% by weight, 5i0230
．． Aqueous colloidal silica sol containing 5% by weight 244.95
was added to the solution while stirring. The substance obtained here is 2, O
K2O・5.9 Na2O* AdzOa・19.6
It is expressed as S 102 .316 HzO.

The reactor was then sealed and heated to 100 °C for 24 h at room temperature.
The mixture was stirred at C for 90 hours. Next, the precipitated powdery crystals are collected under reduced pressure, and then the crystals are collected until the pH of the washing solution is about 8-8.
It was washed with distilled water until the temperature reached 9 and dried at 120° C. for 16 hours.

Next, copper ion exchange was performed in the same manner as in the preparation method for the substance (1) of the present invention.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the chabasite group. Also, elemental analysis revealed that the Si/A/atomic ratio was 3.
．． 59, the copper content is 2.6% by weight and the material is 0.85CuO-0,29 and 20-0.36Na20-
A120. ” 7.18SiO2・13.20H20
It is indicated by.

Sodium aluminate 1 containing 6.8% by weight of Na2O2, 43.2% by weight of AlzO3 and 0.5% by weight of HzO3
4.37y and 14.22 da of sodium hydroxide containing 77.5% by weight of Na2O were dissolved in 119.81f of distilled water. This solution was added with stirring to an aqueous colloidal silica sol 8'8.54f containing 0.4% by weight of Na2O, 5i0230.5% by weight. The substance obtained here is 4, ONa2O: Al1203: 2.88102
:187.4 HzO.

The reactor was then sealed and heated to 100 °C for 24 h at room temperature.
The mixture was stirred at C for 65 hours. Next, the precipitated powdery crystals are collected under reduced pressure, and then the crystals are collected until the pH of the washing solution is about 8 to 8.
It was washed with distilled water until the temperature reached 9 and dried at 120° C. for 16 hours.

Next, add 118g of 0.04M copper sulfate aqueous solution to this crystal 5 da.
After adding /, the pH in the system was adjusted to 6.9 using 10% caustic soda, and the mixture was stirred at room temperature for 4 hours to perform an ion exchange reaction. After the ion exchange reaction was completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water until copper ions and sulfate groups were no longer detected, and then dried at 120''C for 16 hours.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the faujasite group. Elemental analysis revealed that the Si/Al atomic ratio was 1.43 and the copper content was 5.4% by weight.

As a result of electron microscopy measurements, the average particle size was 2. OI1m and the material is 0.88CuO-0,62Na20-Ag203-2.
86SiO2-6,08H20.

Reference material (b) A precursor zeolite was obtained using the same preparation method as in reference material (a). Next, add 0 to the zeolite 5f obtained in this way.
．． After adding 60ml of 16M copper sulfate aqueous solution, the pH in the system
was adjusted to 6.9 using 10% caustic soda, and then heated to 4 at room temperature.
The mixture was stirred for hours to perform an ion exchange reaction. After the ion exchange reaction was completed, the reaction solution was filtered, and the obtained crystals were washed with distilled water until copper ions and sulfate groups were no longer detected.
Dry at °C for 16 hours.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the faujasite group. Further, elemental analysis revealed that the Si/Al atomic ratio was 1.43 and the copper content was 9.9% by weight.

As a result of electron microscopy measurement, the average particle diameter was 2.0 μm,
The substance is 0.70CuO-0,3ONa20-A1203 ・2
．． 86SiO□-5,52H20.

Na2O26.3% by weight, A12034 B, 2% by weight
15y of sodium aluminate containing 0.5% by weight of H2O and 21.551% of sodium hydroxide containing 77.5% by weight of Na2O were dissolved in 262.93f of distilled water. Kono solution is Na2O9.2% by weight5iO229.0% by weight
was added to an aqueous solution of sodium silicate containing 870,66 f with stirring. The material obtained here is 13.9 N
azO・A403628.25102・470.9
Indicated by H2O.

The reactor was then sealed and heated to 100 °C for 24 h at room temperature.
The mixture was stirred at C for 24 hours. Next, the precipitated powdery crystals are dried under reduced pressure, and then the crystals are washed until the pH of the washing solution is approximately 8 to 8.
It was washed with distilled water until the temperature reached 9 and dried at 120°C for 16 hours.

Next, copper ion exchange was performed in the same manner as in the preparation method for the substance (1) of the present invention.

The powdery substance thus obtained was confirmed to be an amorphous aluminosilicate by X-ray diffraction.

Also, elemental analysis revealed that the Si/Al atomic ratio was 3.04, the copper content was 4.7% by weight, and the substance was 0.58C110-0,47Na20-A1203-6.
．． 088iO2-9,92H20.

Reference substance (d) A precursor zeolite was obtained in the same manner as in the preparation method of reference substance (a). Next, 100 w of a 0.048 M copper sulfate aqueous solution was added to the zeolite 5f obtained in this way, and the pH in the system was adjusted to 4.2 using 10% hydrochloric acid, and the pH was adjusted to 75°.
The mixture was stirred at C for 4 hours to perform an ion exchange reaction. After the ion exchange reaction is completed, the reaction solution is filtered, and the obtained crystals are washed with distilled water until copper ions and sulfate groups are no longer detected.
Dry at 120'C for 16 hours.

The powdery substance thus obtained was confirmed to be an amorphous aluminosilicate by X-ray diffraction. Further, elemental analysis revealed that the Si/Al atomic ratio was 1.43 and the copper content was 5.5% by weight. As a result of electron microscopy measurement, the average particle diameter was 2.0 μm, and the substance was 0.39Cuo ” 0.61 Na2O” Al2O
3.2.86S 102"5.94H20.

Reference substance (e) Na20 26.3% by weight, j'J! 35.1' of sodium aluminate containing 20343.2% by weight and 30.5% by weight of H2O and 29.89 f/ of sodium hydroxide containing 77.5% by weight of Na2O were dissolved in 194.2F of distilled water. Kono solution is Na2O9.2% by weight, 5iO22
Aqueous solution of sodium silicate containing 9.0% by weight 62.0
7 g with stirring. The substances obtained here are: 4.I Na2O.Alz03.2. O3i02・92
．． 7H20.

The reactor was then sealed and stirred at room temperature for 3 hours and then at 60°C for 3 hours. Next, the precipitated powdery crystals were collected in a vacuum under reduced pressure, washed with distilled water until the pH of the washing solution became about 8 to 9, and dried at 120°C for 16 hours.

Next, 60 ml of 0.16M copper nitrate aqueous solution was added to this crystal 5f, and the pH of the system was adjusted to 6.0 using 10% caustic soda.
9 and stirred at room temperature for 4 hours to perform an ion exchange reaction. After the ion exchange reaction was completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water until copper ions and nitrate groups were no longer detected, and then dried at 120''C for 16 hours.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the faujasite group. Further, elemental analysis revealed that the Si/Al atomic ratio was 1.15 and the copper content was 10% by weight.

As a result of electron microscopy measurement, the average particle diameter was 1.8 μm, and the substance was 0.68CuO-0,37Na20·A1203-2.
305iO2-4,91H20.

Reference substance (f) A precursor zeolite was obtained in the same manner as the preparation method of reference substance (e). Next, 100 tons of a 0.048M copper sulfate aqueous solution was added to the zeolite 5f obtained in this way, and the pH in the system was adjusted to 4.2 using 10% hydrochloric acid, and the pH was adjusted to 75°C.
The mixture was stirred at C for 4 hours to perform an ion exchange reaction. After the ion exchange reaction is completed, the reaction solution is filtered, and the resulting crystals are washed with distilled water until no copper ions or sulfate groups are detected.
Dry at 120'C for 16 hours.

The powdery substance thus obtained was confirmed to be an amorphous aluminosilicate by X-ray diffraction. Further, elemental analysis revealed that the Si/A/atomic ratio was 1.15 and the copper content was 5.7% by weight. As a result of electron microscopy measurement, the average particle diameter was 1.8 μm, and the substance was 0.36CuO-0,64Na20-A1203 ・2
．． 30SiO2-5,26H20.

Na2O26.8% by weight, A40348.2% by weight and H
Sodium aluminate 15 containing 2O80.5% by weight
Sodium hydroxide containing f and Na2O77.5% by weight
．． 481 and distilled water sr4. Dissolved in sa. The Kono solution was added to an aqueous colloidal silica sol 249, 84 containing 0.4% by weight of Na2O and 30.5% by weight of 5iO2 with stirring. The substance obtained here is 12.2Na20-A1203-20.05iO2'4
96H20.

The reactor was then sealed and kept at room temperature for 24 hours and then at 100°C.
The mixture was stirred for 24 hours. Next, the precipitated powder crystals were collected under reduced pressure in F, and the crystals were collected until the pH of the washing solution was about 8 to 9.
It was washed with distilled water until dry and dried at 120'C for 16 hours.

Next, after adding 118 ml of 0.5M copper sulfate aqueous solution to this crystal 5f, the pH in the system was adjusted to 4.2 using 10% sulfuric acid, and the mixture was stirred at 70°C for 4 hours to perform an ion exchange reaction. Ta. After the ion exchange reaction was completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water until copper ions and sulfate groups were no longer detected, and then dried at 120°C for 16 hours. The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the analcyme group. Furthermore, elemental analysis revealed that the Si/A/atomic ratio was 2.4.
The content of 1A is 2.0% by weight, and the material is 0.20CuO-0,8ONa20-A/203-4.
825iO2-10,17H20.

A precursor zeolite was obtained in the same manner as the method for preparing the substance (5) of the present invention. Using these materials, ion exchange reactions were performed with zinc, tin, iron, nickel, magnesium, or cobalt, respectively, according to the copper ion exchange method described above. That is, in the case of zinc for the above zeolite powder pot 5y,
30 ml of 0.16M zinc nitrate aqueous solution, 80 ml of 0.08M stannic chloride aqueous solution for 1 tin, 30 ml of 0.18M ferric chloride aqueous solution for 1 iron, 100 ml of 0.05M nickel nitrate aqueous solution for nickel , 100 wtl of magnesite aqueous solution were added to each, and a 10% caustic soda aqueous solution was added to adjust the pH in the system to 4.2.
Stirred at 70'C for 4 hours. After ion exchange, the powder was filtered, washed with 200 tel distilled water, and incubated at 120°C for 1 hour.
It was dried for 6 hours. It was confirmed by X-ray diffraction that each of the obtained powders was a crystalline zeolite belonging to faujasite.

Furthermore, elemental analysis revealed that the Si/Al atomic ratio of these powders was 2.58.

The table below shows the metal content and composition of each substance thus obtained.

In addition, in the following test examples, the control efficacy is determined by visually observing the diseased state of the test plants at the time of investigation, that is, the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, l' -5
J, ``4'' if about 10%, ``3'' if about 30%, ``2'', 70%
If the degree of disease is observed, it is scored as "1", and if it is higher than that and there is no difference from the disease onset state when no compound is tested, it is scored as "0".
Indicated by 0.

Test Example 1 Cucumber and disease control test (preventive effect) Plastirag pots were filled with sandy loam, and cucumbers were sown and grown in a greenhouse for 20 days.

A test drug prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration on cucumber seedlings that had developed their second true leaves.
It was sprayed on the foliage so that it adhered sufficiently to the foliage. After spraying, a spore suspension of cucumber and disease bacteria was sprayed and inoculated.

After inoculation, the plants were incubated at 20° C. in a humid environment for one time, and then grown under lighting for 5 days to investigate their pesticidal efficacy. The results are shown in Table 1.

Table 1 %1 Basic copper chloride (hereinafter the same) f2 Bordeaux liquid (mixture of copper sulfate and quicklime) (hereinafter the same) Test Example 2
Tomato late blight control test (preventive effect) A plastic pot was filled with sandy loam, tomatoes (ponchirosa) were sown, and grown in a greenhouse for 20 days. Tomato seedlings that have developed their 2nd to 3rd true leaves, dilute the test chemical in the form of a hydrating powder with water to the desired concentration according to Formulation Example 1, and spray it on the foliage so that it fully adheres to the leaf surface. did.

After spraying, a spore suspension of Phytophthora tomato was sprayed and inoculated.

After inoculation, the plants were incubated at 20° C. in a humid environment for one time, and then grown under lighting for 5 days to investigate their pesticidal efficacy. The results are shown in Table 2.

Table 2 Test Example 3 Radish black soot disease control test (preventive effect) A plastic pot was filled with sandy loam, and radish (60-day radish) was sown and grown in a greenhouse for 6 days. A test chemical prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on radish seedlings with developed cotyledons so as to sufficiently adhere to the leaf surface. After the spraying, a spore suspension of the radish rust fungus was sprayed and inoculated. After inoculation, 18
After growing in a humid environment at 1°C for 3 days, the plants were grown under lighting for 3 days, and their pesticidal efficacy was investigated. The results are shown in Table 3.

Table 3 Plastic pots were filled with sandy loam, and cucumbers (Sagami half day) were sown and grown in a greenhouse for 35 days. Thereafter, the test drug prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on the leaves so as to sufficiently adhere to the leaf surface. After spraying, stay in the greenhouse for 7 days (20°C during the day, 17°C at night)
After cultivation at 10°C (°C), the plants were inoculated by spraying with a spore suspension of the cucumber spot bacterium. After inoculation, the seeds were kept in a humid environment for about 24 hours, and then grown for 10 days under the above greenhouse conditions, and the control effect was calculated. The results are shown in Table 4.

Table 4 Test Example 5 Rice blight control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 33) was sown and grown in a greenhouse for 70 days. A test chemical prepared as a wettable powder according to Formulation Example 2 was diluted with water to a predetermined concentration, and was sprayed on rice seedlings so that it would sufficiently adhere to the ears.

After spraying, the plants are air-dried and sprayed with rice blight spore suspension.
Inoculated. After inoculation, the plants were kept in a dark and humid environment at 23°C for 1 day, and then allowed to develop for 9 days in a greenhouse at 27°C to investigate the control efficacy. The results are shown in Table 5.

Table 5 Test Example 6 Cucumber anthracnose control test (preventive effect) A plastic pot was filled with sandy loam, and cucumbers (Sagami Hanshiro) were sown and grown in a greenhouse for 14 days. A test drug prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed onto cucumber seedlings with developed cotyledons so as to sufficiently adhere to the leaf surface. After spraying, a spore suspension of cucumber anthracnose was sprayed and inoculated. After inoculation, the plants were left at 23° C. under humid conditions for 18 days, and then grown under lighting for 4 days to investigate their pesticidal efficacy. The results are shown in Table 6.

Table 6

Claims (2)

[Claims] (1) An agricultural and horticultural sterilizer characterized by containing as an active ingredient one or more crystalline zeolites selected from the group consisting of the faujasite group, the shabasite group, and the philipsite group represented by the following general formula. agent. aCuO・(1-a)M_2O・Al_2O_3・bS
iO_2·cH_2O [In the formula, M represents a sodium atom and/or a potassium atom, and a, b and c each represent a numerical value within the following range. 0<a≦1, 3<b≦12, 0≦c≦20] (2) An agricultural and horticultural fungicide characterized by containing as an active ingredient one or more crystalline zeolites selected from the group consisting of the faujasite group and the philipsite group represented by the following general formula. aCuO・(1-a)M_2O・Al_2O_3・b′
SiO_2.cH_2O [In the formula, M represents a sodium atom and/or a potassium atom, and a, b' and c each represent a numerical value within the following range. 0<a≦1, 3.5<b'≦8, 0≦c≦20]