JPH0436207A - Agricultural and horticultural germicide - Google Patents

Abstract

PURPOSE:To obtain a germicide, containing crystalline zeolite selected from the mordenite group and pentasil type as an active ingredient, capable of reducing the amount of chemical used and improving phytotoxicity to crops and applicable to even crops in which metal-containing germicides could not be used. CONSTITUTION:An agricultural and horticultural germicide containing crystalline zeolite selected from the mordenite group and pentasil type expressed by the formula (M is Na and/or K; 0<x<=1; 8<y; 0<=z<=20) as an active ingredient. The aforementioned compound expressed by the formula is produced by, e.g. mixing an aqueous solution of sodium aluminate with an aqueous solution of sodium silicate at a prescribed concentration ratio in an aqueous solution of NaOH, carrying out hydrothermal synthesis, providing zeolite which is a precursor and subjecting the resultant zeolite to ion exchange thereof with a copper salt in water or an alcohol. The aforementioned germicide is used in an amount of 0.3-300g/a active ingredient by a method for foliar spraying, soil treatment, seed disinfection, etc.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to an agricultural product containing as an active ingredient one or more crystalline zeolites selected from the mordenite group and the pentasil type, represented by the following general formula [1]. Regarding horticultural fungicides.

<Prior Art> Conventionally, inorganic copper agents such as Bordeaux liquid have been used in the fields of fruit trees, vegetable crops, etc. Further, Japanese Patent Publication No. 6123164 describes certain copper-substituted aluminosilicates.

Further, JP-A-1-156905 describes certain copper-substituted zeolites, which are crystalline zeolites belonging to the faujasite group, the noyabasite group, or the phillipsite group, and therefore are not applicable to the present invention. It is completely different from zeolite.

<Problems to be Solved by the Invention> Conventional copper fungicides have limited range of application because they are effective against a narrow range of diseases and cause chemical damage to crops.

Furthermore, conventional copper-substituted aluminosilicates have insufficient effects per copper and cannot be said to be necessarily satisfactory, and there is a long-awaited development of high-performance drugs that are less harmful and are effective at lower doses. <Means for solving the problem> Under these circumstances, as a result of intensive studies to find a high-performance drug that causes less drug damage and is effective at a low dose, the present inventors discovered that a crystalline zeolite selected from the mordenite group and the pentasil type represented by the general formula (1) has extremely excellent bactericidal activity and does not exhibit problematic phytotoxicity, leading to the present invention.

That is, the present invention is based on the general formula % [where M represents a sodium atom and/or a potassium atom, and x, y and 2 each represent a numerical value within the following range.

0<x≦1.8<yO≦2≦20] An agricultural product containing as an active ingredient one or more crystalline zeolites selected from the mordenite group and the pentasil type (hereinafter referred to as the substance of the present invention). Provide horticultural fungicides.

The content of copper in the substance of the present invention can be arbitrarily determined, but is preferably up to an amount that can replace M8 with a copper atom in the general formula.

Next, a method for producing the substance of the present invention will be described.

The substance of the present invention can be produced by hydrothermal synthesis 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 doing this, and then these zeolites and a copper salt are subjected to an ion exchange reaction in water or alcohol.

Examples of the copper salt used in the above ion exchange reaction include mineral acid salts such as cupric chloride, cupric sulfate, and cupric nitrate; organic acid salts such as cupric acetate and cupric formate; and ammonia salts. Examples include copper complex salts, and preferably mineral acid salts such as cupric chloride, cupric sulfate, and cupric nitrate.

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 (εrwinia carotovo)
ra), solanaceae bacterial wilt (Pseudomonas
solanaclearum), bacterial spot disease of cucumbers (Pseudomonas button-row hanging box), and bacterial spot disease of vegetables (Pseudos+onas)
culicola), black rot (Xanthomona
s group sin adandan), root cancer φ disease 7 tumefa
tomato canker disease), tomato canker disease
Bacterial rice blight disease (Pseudomo)
nas Honghuifeng), Tobacco wildfire disease (Pseudomo)
Nasda fallen rainbow), mandarin canker disease (Xanthoso
Xanthosonas chinensis), downy mildew of vegetables and radish (Xanthosonas abrassica)
e) Spinach noheto disease (Asahi Mosquito Crazy Rainbow A” Salmon Hakoji Nami),
Tobacco mildew (A tabacina)
, cucumber downy mildew (Pseudo eronos o)
ra cubensis) on grapes (■PhythoracactorulI), downy mildew on Apiaceae plants (■Kyosamedai gall '■Hiroshi), late blight on apples, strawberries, and ginseng (PhtohthoracactorulI),
Gray late blight of tomatoes and cucumbers (7cinnamomi)
, Late blight of potatoes, tomatoes, and eggplants (L parallel plate anal a 1
nfestans), Tobacco, Broad Beans, and Fugi Epidemiology
1 cotianae), spinach damping-off (pi
sp, ), cucumber seedling damping-off (bdanium ah
anidermatum), wheat brown snow rot (Pi
thius dan), Tobacco seedling damping-off disease (h tillage - Akane Tsutomun)
skin slap), dice Pythium Rot (im
parallel anus der+eatum, L" and other anus concave m, P,
rrre ulare, P.

P. ultiman), rice blast (Hwatacularia nijiuyo), sesame leaf blight (
Cochliob (snoring), apple scab (Venturia), rot (Val)
samali), leaf spot disease (Alternari)
a wadan), pear black spot (1 stop rnaria)
kikuchiana), Venturia blight (Venturia
citrus black spot (Niji-nami-do-den-e-ri-dandan), persimmon anthracnose disease (powdery mildew), leaf fall disease (
Cercos ora kaki, M cos ha
erella nawae), Fudo late rot disease (Gl
omerella c.
``Ha Wataru C'' annami), leaf blight (Himidaru Rainbowtan tritici)
, haeria nodo
rum) anthracnose disease of cucurbits (Colletotrichu
m d) Vine blight (hNamitsujizen anal ridge area ugly 1 n), tomato ring spot disease (Alternaria 5olani)
, Tobacco red star disease (Alternaria category) - Anthracnose disease (Col 1etotrichu++ ta)
bacua+), brown spot of sugar beet (7betico
la), potato summer wasting disease (Alternaria
brown spot disease of groundnuts
idicola), soybean brown spot (C.
olletotrichum St3. ), purpura (
7kon kikuchii), etc.

The substance of the present invention can be used as an agricultural and horticultural fungicide in fields, paddy fields, orchards, tea gardens, pastures, lawns, etc., and can be used in combination with other plant disease control agents to increase the bactericidal effect. We can also expect an increase.

Furthermore, it can be used in combination with insecticides, acaricides, nematicides, 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 mixed with a solid carrier, liquid carrier, surfactant, or other formulation auxiliary agent. The content of the substance of the present invention in the formulation used in granules, wettable powders, suspensions, powders, etc. is 0.1 to 9.
9.9%, preferably 1-99%.

Examples of the solid carriers mentioned above include kaolin clay, attabulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob flour, corn husk flour, urea, ammonium sulfate, synthetic hydrous silicon oxide, etc. Examples of the carrier include fine powder or granules, and examples of the liquid carrier 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 bronocopolymers ? -, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and other nonionic surfactants. Strengthening agents for formulations include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), and PAP.
(acidic isopropyl phosphate), etc.

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.

Ill1 the substance of the present invention! When used as an active ingredient in an horticultural fungicide, the amount of the active ingredient to be applied depends on the target crop, target disease, degree of disease occurrence, formulation form, application method, application time, weather conditions, copper content, etc. Although it varies, usually 0.3 to 600 g per are, preferably 0.3 to 30
0g, and when applying a wettable powder, suspension agent, etc. diluted with water, the application concentration is 0.015 to 1.5%, preferably 0.03 to 0.6%, and a powder, Granules etc. are applied as is without any dilution.

<Examples> The present invention will be described in more detail below, 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 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 A suspension is obtained by mixing 50 parts of the substance of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 44 parts of water and wet-pulverizing the mixture until the particle size of the active ingredient becomes 5 microns or less. It will be done.

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 47 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.

Kitosho Chiba (1) Model Night (61ONAA ■ Tosoh) 0.04 to 5g
After adding 118d of M copper sulfate aqueous solution, the pH in the system was adjusted to 10.
% sulfuric acid to 4.2, and stirred at 70°C for 4 hours to perform an ion exchange reaction. After the ion exchange reaction is completed,
The reaction solution was filtered, the resulting crystals were washed with distilled water until copper ions and sulfate groups were no longer detected, and then incubated at 120"C for 1 hour.
It was dried for 6 hours.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the mordenite group. Also, elemental analysis revealed that the Si/Al atomic ratio was 5.
．． 5. The content of copper is 2.6% by weight, and the relevant substances are: 0.386CuO・0.614NatO・AlzO:+
・11.0SiOz ・6.20H! Denoted by O.

Kinogaichi! (2) Model Night (64ONAA ■ Tosoh) 0.04 per 5g
After adding 118ml of M copper sulfate aqueous solution, the pH in the system was lowered to 10.
% sulfuric acid to 4.2, and stirred at 70°C for 4 hours to perform an ion exchange reaction. After the ion exchange reaction is completed,
The reaction solution was filtered, the obtained crystals were washed with distilled water until copper ions and sulfate groups were no longer detected, and then incubated at 120°C for 1 hour.
It was dried for 6 hours.

The powdery substance thus obtained was confirmed by X-ray diffraction to be a crystalline zeolite belonging to the mordenite group. Also, elemental analysis shows that the Si/A+ atomic ratio is 1.
0.0. The content of copper is 1.4% by weight, and the material is 0.325CuO.0.675NazO.Al2O3.
20.05iOz: 5.80H,O.

First purchase of Kito plate (3) First, a raw material liquid having the following composition was prepared.

Solution A: 162g of distilled water, 16.7g of sulfuric acid, Ah (SO
4) 18H,040,Og(n-Pr) aNBr
20.8 g Solution B: Distilled water 119.7 g, No. 3 sodium silicate 186.3 g Solution C: Distilled water 281.7 g, Sodium chloride 70.7
g Solutions A and B were simultaneously added dropwise to the above Solution C and mixed with vigorous stirring. The pH at the end of mixing was 9.6. The mixture was placed in a 1.52 stainless steel autoclave and heated at 160'C for 20 hours at 400r.

Hydrothermal synthesis was carried out while stirring at a rotation speed of 1,000 m or more. After cooling, filter and add distilled water of about 71 C! Washing and filtration were repeated until no ions were detected. Further, the obtained white solid was dried at 120°C for 16 hours. The crystals were then calcined at 500 to 550°C for 4 hours under air circulation to obtain white powdery crystals.

Next, 118 d of a 0.04 M copper sulfate aqueous solution was added to 5 g of this crystal, and 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. . 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 sulfur M radicals 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 pentasil group! Approved. Also, elemental analysis revealed that the Si/Al atomic ratio was 7.
．． 87, the copper content is 3.1% by weight, and the substance is 0.592CuO・0.408Naz(lA]toz
It is indicated by i5.74sioz '5.208zO.

Comparative Kinso (a) 14.37 g of sodium aluminate containing 26.3% by weight of Nazo, 43.2% by weight of AIzOi and 30.5% by weight of H, and 14.22 g of sodium hydroxide containing 77.5% by weight of NazO. was dissolved in 119.81 g of distilled water. This solution was mixed with NazOO, 4% by weight 5iOJ0
．． 33.54 g of aqueous colloidal silica sol containing 5% by weight
was added while stirring.

The material obtained here is 4.0NazO: Altos: 2.8SiO
t: 137.4HzO.

The reactor was then sealed and kept at room temperature for 24 hours and then at 100°C.
The precipitated powder crystals were then collected by filtration under reduced pressure.
The sample was washed with distilled water until drying at 120°C for 16 hours.

Next, 0.16 M copper sulfate aqueous solution 6 (ld) was added to 5 g of the crystals thus obtained, and the pH of the system was adjusted to 6.9 using 10% caustic soda, followed by stirring at room temperature for 4 hours. After the ion exchange reaction was completed, the reaction solution was heated for 21 hours, and the obtained crystals were washed with distilled water until copper ions and nitrate groups were no longer detected, and then incubated at 120°C for 1 hour.
It was dried for 6 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, the copper content was 9.9% by weight, and the substance was 0.70CuO・0.3ONazOHAlzOi'
It is expressed as 2.86S+Oz ・5.528zO.

Comparative Kinship (b) 35.4 g of sodium aluminate containing 26.3% by weight of Nazo, 43.2% by weight of AlzOs and 8.030.5% by weight and sodium hydroxide containing 77.5% by weight of Nano29. 89 g was dissolved in 194.2 g of distilled water. This solution was mixed with Nazo 9.2% by weight, 5in1 2
Aqueous solution of sodium silicate containing 9.0% by weight 62.0
7g was added with stirring. The substance obtained here is 4, INazO'A1zOs H2,05iOz'
92.7H! Indicated by 0.

Next, the reactor was sealed and stirred at room temperature for 3 hours and then at 60°C for 3 hours.Then, the precipitated powder crystals were collected by filtration under reduced pressure. Washed with distilled water until the temperature was ~9 and dried at 120"C for 16 hours.

Next, 60 d of 0.16 M copper sulfate aqueous solution was added to 5 g of the crystals obtained in this way, and the pH of the system was adjusted to 6.9 using 10% caustic soda, and the mixture was stirred at room temperature for 4 hours to ionize. An exchange reaction was performed. 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 revealed that the Si/Al atomic ratio was 1.15, the copper content was 10% by weight, and the substance was 0.63CuO・0.37NazO-AlzOz・
It is represented by 2.30SiOz·4.91H,O.

In the following test example, the control efficacy was determined by visually observing the disease state of the test plant 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 were observed, it was evaluated as "5". 10%
If it is recognized to a certain extent, it will be ``4'', if it is recognized to be around 30%, it will be r3.
J, if it is observed in about 50%, it is ``2'', if it is observed in about 70%, it is ``1'', and if there is no difference from the disease onset state when no compound is tested, it is ``0'', and it is evaluated on a 6-level scale. and 5. 4. 3. 2. 1. 0
Indicated by

Test Example 1 Cucumber and disease control effect (preventive effect) Plasti and kubonoto were filled with sandy loam, and cucumbers were sown and grown in a greenhouse for 20 days. To cucumber seedlings that had developed their second true leaves, a test drug made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on the foliage so that it adhered sufficiently to the leaf surface. . After spraying, a spore suspension of cucumber and disease bacteria was sprayed and inoculated. After inoculation, the plants were grown under 1B1 at 20°C under high humidity, and then grown under lighting for 5 days to investigate the control efficacy. The results are shown in Table 1.

Table 1 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. A test chemical prepared as a hydrating powder according to Formulation Example 1 is diluted with water to a specified concentration on young tomato seedlings that have developed their 2nd to 3rd true leaves, and sprayed 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 grown under 1B1 at 20°C and high humidity, and then grown under lighting for 5 days to investigate the control efficacy. The results are shown in Table 2.

(Mixture of copper sulfate and quicklime) (The same applies hereinafter) The mixture was adjusted to a prescribed concentration as shown in the table below, and was sprayed on the foliage so that it would sufficiently adhere to the leaf surface. After the spraying, a spore suspension of the radish rust fungus was sprayed and inoculated. After inoculation, the plants were grown under 1B1 at 18°C under high humidity, and then grown under lighting for 3 days to investigate the control efficacy. The results are shown in Table 3.

Table 3 Test Example 3 Radish black soot 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. Test Example 4: Rice rice blight control test (Table 1): A test drug prepared as a wettable powder according to Formulation Example 1 was diluted with water to young radish seedlings with expanded cotyledons.
Preventive effect) Fill plastic pots with sandy loam and add rice (
Near lol! 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 were air-dried and then sprayed with a spore suspension of rice blight and 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 4.

Table 4 <Effects of the Invention> The agricultural and horticultural fungicide of the present invention is highly effective against various plant diseases, so the amount of chemicals used can be reduced, and phytochemical damage to common crops can be significantly reduced. It has the great advantage of being fully applicable to crop fields where it has been difficult to use existing metal-containing fungicides such as Bordeaux liquid.

Claims (1)

[Scope of Claims] An agricultural and horticultural fungicide characterized by containing as an active ingredient one or more crystalline zeolites selected from the mordenite group and the pentasil type, represented by the following general formula. xCuO・(1-x)M_2O・Al_2O_3・yS
iO_2.ZH_2O [In the formula, M represents a sodium atom and/or a potassium atom, and x, y and z each represent a numerical value within the following range. 0<x≦1, 8<y0≦z≦20]