AU608038B2

AU608038B2 – A copper zeolite fungicide composition
– Google Patents

AU608038B2 – A copper zeolite fungicide composition
– Google Patents
A copper zeolite fungicide composition

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Publication number
AU608038B2

AU608038B2
AU20547/88A
AU2054788A
AU608038B2
AU 608038 B2
AU608038 B2
AU 608038B2
AU 20547/88 A
AU20547/88 A
AU 20547/88A
AU 2054788 A
AU2054788 A
AU 2054788A
AU 608038 B2
AU608038 B2
AU 608038B2
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Australia
Prior art keywords
substance
group
formula
copper
hours
Prior art date
1987-09-04
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AU2054788A
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Inventor
Shigeko Kimura
Masaru Kitamura
Masato Mizutani
Yukio Oguri
Hiroshi Sato
Masao Sirosita
Youichi Umada
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Sumitomo Chemical Co Ltd

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Sumitomo Chemical Co Ltd
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1987-09-04
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1988-08-09
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1991-03-21

1988-08-09
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Sumitomo Chemical Co Ltd

1989-03-09
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1991-03-21
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1991-03-21
Publication of AU608038B2
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2008-08-09
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Classifications

C—CHEMISTRY; METALLURGY

C01—INORGANIC CHEMISTRY

C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C

C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination

C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof

C01B39/026—After-treatment

A—HUMAN NECESSITIES

A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING

A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS

A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

A01N59/16—Heavy metals; Compounds thereof

A01N59/20—Copper

Description

A
~1
I
ii
AUSTRALIA
PATENTS ACT 1952 COMPLETE SPECIFICATION Fv)rm
(ORIGINAL)
FOR OFYXCF USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: IThis do0cuIment contins the Camnendments made under 53ec lion 49 and is correct for printing, Priority; Related Art: p TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: SUMITOMO CHEMICAL COMPANY,
LIMITED
15,
HIGASHI-KU
OSAKA
JAPAN
Actual Invehtor:, Address for Service: GRIFFITH HACK CO., 601 St, Kilda Road, Melbourne, Victoria 3004, Australia, Complate Specification for the invention entitl~ed: A CoP~ zscIrUTI~D The following statement i~s a full. description of this invention including the best method of performing it known to me;-
SI
U
SI
1 The present invention relates to an agricultural and horticultural fungicide containing as an active ingredient at least one crystalline zeolite selected from the group consisting of faujasite group, chabazite group and phillipsite group represented by the formula (hereinafter referred to as the present substance), aCu0-(l-a)M 2 OAl 2 0 3 bSiO 2 cH 2
O
9 o? 9 o o o o 9 9J 9 o er9 9o 0 i t O, 0i 4 9 00r wherein M represents a sodium and/or potassium atom, and a, b and c fall in the following ranges, 0 1, 3 b 12, 0 c Among the present substances, what is particularly superior in terms of the controlling activity is at least one crystalline zeolite selected from the group consisting of faujasite group and phillipsite group represented by the formula, aCuO- M 2 0-A1 2 0 3 bSiO 2
CH
2 0 4 wherein M represents a sodium and/or potassium atom, and a, b and c fall in the following ranges, 2 i i.Lj 0 a 1, 3.5 b 8, 0 c 1 Hitherto, as the fungicide for fruit trees, vegetables, etc., inorganic copper-containing chemicals such as a Bordeaux mixture, etc. have been used.
However, these known fungicides are not satisfactory because they show efficacy only against narrow range of deseases and the phytotoxicity to crops limits the range of the application. Consequently, developing high-performance chemicals which give little phytotoxicity and are effective at a low dosage rate has been desired.
In recognition of the situation, the present inventors have extensively studied to find chemicals which have an excellent activity against various diseases of fruit trees, vegetables, etc. and can safely be applied to crops, and as a result, have surprisingly found that the present substance has an excellent fungicidal activity and yet shows no problematic phytotoxicity. The present inventors thus attained to the present invention.
JP-A-59-186908 discloses that a product obtained by copper ion exchange of aluminosilicate can be used as an agricultural and horticultural fungicide. In reality, however, the copper-containing aluminosilicate disclosed in the above literature does not have a strong fungicidal activity per copper content and it cannot compensate the defect of the conventional inorganic 3 1 copper-containing chemicals.
The present inventors have extensively studied to develop a chemical having sufficiently high fungicidal activity per copper content enough to be highly effective at a low dosage rate of copper, and as a result, have found that the crystalline zeolite represented by the foregoing formula has an extremely high activity per copper content.
Comparing the activity per copper content of the existing inorganic copper-containing chemicals with that of the present substance shows that, although depending upon diseases to be controlled, the present substance has an activity more than 10 times as high as the existing chemicals, as described in the following 15 examples about many diseases. Such a marked development in the activity per copper content is epoch-making, and highly active copper-containing chemicals such as the present substance have not been known in spite of studies on copper fungicides for more than the past 100 years.
A great improvement in the activity per co per content results in various advantages in controlling o4* Crop diseases. That is, since the agricultural and horticultural fungicide of the present invention exhibits 25 an excellent activity against various plant diseases, it has a number of advantages as follows: Its dosage rate can be reduced because the phytotoxicity to crops can be markedly improved. It can 4 I ii r 3 _~LL IYIL–LL— .I r~ ;lil_ 1 be satisfactorily applied to various crops to which the existing metal-containing fungicides such a a Bordeaux mixture, etc. cannot be applied. And because of a great improvement in its activity per copper content, it has an advantage that it can be applied without increasing a residual copper content to a field containing a large amount of residual copper in the soil.
The copper content of the present substance can be determined optionally, but preferably, it is at most the amount of copper atoms when all of M 2 in the foregoing formula are substituted by copper atoms.
The present substance can be obtained by a known method. An example thereof is a method comprising adding an aqueous sodium or potassium aluminate solution and an aqueous sodium or potassium silicate solution in a prescribed concentration ratio to an aqueous caustic soda or caustic potash solution, carrying out hydrothermal synthesis to produce zeolite, the precursor of the present substance, followed by ion-exchanging the zeolite with a water-soluble copper salt in water or an alcohol. The water-soluble copper salt used in this reaction includes for example mineral acid salts of copper such as cupric chloride, cupric sulfate, 25 cupric nitrate, etc. Further, organic acid salts cupric acetate, cupric formate), ammonia-copper complex salts, etc. may also be used.
Because the present substance exhibits an 5 1 excellent effect against plant diseases, it can be used in various applications as an active ingredient for agricultural and horticultural fungicides.
As examples of plant diseases which can be controlled by the present substance, there may be mentioned the following diseases: Bacterial soft ,ot of various vegetables (Erwinia carotovora), bacterial wilt of solanaceous plants (Pseudomonas solanacearum), angular leaf spot of cucumber (Pseu.\monas lachrymans) bacterial leaf spot of vegetables (Pseudomonas syringae pv. maculicola), black rot of vegetables (Xanthomonas campestris), Crown gall of vegetables (Agrobacterium tumefaciens) bacterial canker of tomato (Corynebacterum michiganense), bacterial grain rot of rice (Pseudomona glumae) wild fire of tobacco (Pseudomonas tabaci) canker of citrus (Xa.4hc.jonas campestris pv. citri) bacterial leaf blight of rice (Xanthomonas oryzae) downy mildew of vegetables and Japanese radish (Peronospora brassicae) downy mildew of spinach (Peronospora spinaciae) downy mildew of tobacco (Peronospora tabacina) downy milde v of cucumber (Pseudoperonospora cubensis) downy mildew of grape (Plasmopara viticola) downy mildew of dropwort (Plasmopara fniva) I late blight of apple, strawberry and ginseng (Fhytophthora cactorum), phytophthora rot of tomato and cucumber (Phytophthora capsici) late blight of pincapple (hytophthora ciniamomi), late blight of potato, tomato and eggplaiat (Phytophthra infestans) late blight of tobacco, broad bean and Welsh onion (Phytophthora -6- 1nicotianae var. nicotianae) damping-off of spinach (Pythium sp.) damping-off of cucumber (Pythiumj aphanidermatum) browning root rot of wheat (Pythium sp.), damping-off off tobacco (Pythium debaryanum) pythium rot of soybean (Pythium aphanidermatum, P. deLbaryanuict, P.
irregulare, P. myriotylun, P. ultimum) blast or rice (Pyricularia 2ryzae helminthosporiun leaf spot of rice (Cochliobolus miyabeanus), scab of apple (Venturia inaecjualia) canker of apple (Valsa mal 1, alternaria leaf spot of apple (Alternaria mali) black spot of pear (Alternaria kikuchiana) scab of pear (Venturia nashizcola) melanose of citrus (Diaporthe citri), anthracnose of Japanese persimmon (Gloeosparium kaki), leaf spot of Japanese persimmon (Cercospora, kaki, Mycosphaerella nawae), ripe rot of grape (CGlomerella cingulata), gray mold of grape (Botrytis cinerea), speckled leaf blotch of wheat (Septoria tritici), glume blotch of wheat (Leptosphaeria nodorum), anthracnose of melons (Coll etotrichum lagenarium) gummy stem blight of melons (Myosphaerella melonis) early blight of tomato (Alternaria solani) brown spot of tobacco (Alternaria longipes) anthracnose of tobacco (Collectotrichum tabacum) cercospora leaf spot of beet (Cercospora beticola), early blight of potato (Alteriiaria solani), brown leaf spot of peanut (Cerco spipra arachidicola) septoria brown spot of soy~bean (Soptoria g ycines), pod and stem blight of soybean (Diaporthe phaseololun), anthracnosea of soybean (Colletotrichum sp.), 7- 4~rrmrulP~ 1 purple stain of soybean (Cercospora kikuchii), etc.
The present substance can be used as an agricultural and horticultural fungicide in plow fields, paddy fields, orchards, tea gradens, pastures, turfs, etc. Also, -he present substance can be used in mixture with other fungicides, insecticides, acaricides, nematocides, herbicide,, plant growth regulators and fertilizers.
When the present substance is used as an active ingredient for fungicides, it may be used as it is without adding any other ingredients. Usually, however, it is formulated before use into granules, wettable powders, suspension formulations, dusts, etc. by mixing with solid carriers, liquid carriers, surface active agents and other auxiliaries for formulation. The content of the present substance in these preparations is from 0.1 to 99.9%, preferably from 1 to 99%.
The solid carriers incl ud fine powders or granules of kaolin clay, attapulgite clay, bentonite, terra abla, pyrophyllite, talc, diatomaceous earth, calcite, corn stalk powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon dioxide, etc. The liquid carriers include water.
S 25 The surface active agents used for emulsification, dispersion, wetting, etc. include anionic surface active agents such as the salt of alkyl sulfates, 8 i. i i, ii I I-L u~ri–irunrri ~i rrrruarir~l Ill i i; ~iir;L~- -1 u~ 1 alkyl(aryl)sulfonates, dialkyl sulfosuccinates, the salt of polyoxyethylene alkylaryl ether phosphoric acid esters, naphthalenesulfonic acid/formalin condensates, etc. and nonionic surface active agents such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. The auxiliaries for formulation include lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.
The application method for the agrici’ltural and horticultural fungicide of the present invention includes for example foliage application, soil treatment, seed disinfection, etc., but usually, the present fungicide may be used by any method used by those skilled in the art.
When the present substance is used as an active ingredient for agricultural and horticultural fungicides, the dosage rate of the active ingredient varies with crops to be protected, diseases to be controlled, degree of outbreak of diseases, preparation forms, application methods, application time, weather conditions, copper contents, etc., but it is usually from 0.3 to 600 g/are, preferably from 0.3 to 300 g/are. When the wettable powders, suspension formulations, etc. are applied in dilution with water, the application concentration of the present substance is from 0.015 to 9 1 preferably from 0.03 to The dusts, granules, etc. are applied as they are without dilution.
The following examples serve to give specific illustrations of the practice of the present invention, but they are not intended in any way to limit ‘.ne scope of the present invention.
First, formulation examples are shown. In the examples, parts are by weight.
Formulation example 1 Thoroughly pulverizing and mixing 50 parts of the present substance, 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide gives a wettable powder.
Formulation example 2 Thoroughly pulverizing and mixing 95 parts of the present substance, 3 parts of calciur lignosulfonate, 2 parts of sodium lauryl sulfate gives a wettable poider.
Formulation example 3 Mixing and wet-pulverizing 50 parts of the present substance, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 44 parts of water so o as to the particle size of the active ingredient is reduced to 5 microns or less gives a suspension formulation.
10 1 Formulation example 4 Thoroughly pulverizing and mixing 5 parts of the present substance, 85 parts of kaolin clay and parts of talc gives a dust.
Formulation example Thoroughly pulverizing and mixing 20 parts of the present substance, 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, parts of bentonite and 48 parts of kaolin clay followed by well kneading with water, granulating and drying gives a granule.
Next, the usefulness of the present substance as an agricultural and horticultural fungicide are shown with reference to the following test examples.
In the test examples, test substances were prepared by the following operations.
Present substance (1) Fifteen grams of sodium aluminate containing 26.3 wt.% of Na20, 43.2 wt.% of Al 2 0 3 and 30.5 wt.% of H20 and 63,85 g of sodium hydroxide containing 77.5 wt.% of Na20 were dissolved in 276.04 g of distilled water.
This solution was added to 352.43 g of an aqueous colloidal silica sol containing 0.4 wt.% of Na20 and 30.5 wt.% of Si0 2 with stirring. The substance thus obtained has the formula, 13.9Na20Al 2 0328.2SiO2*470.gH9 2 0 Then, the reactor was closed tightly, the 11 1 substance charged therein was sti&’red tirstly at room temperature for 24 hours and th 100 0 C for 24 hours.
Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120 0 C for 16 hours.
To 5 g of these crystals were added 118 ml of a 0.04 M aqueous copper sulfate solution. Then, the pH of the system was adjusted to 4,2 with 10% sulfuric acid and ion exchange was carried out with stirring at 0 C for 3 hours. After the ion exchange had been completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water until copper ions and sulfate radicals were not detectable and dried at 120ac for 16 hours.
The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to faujasite group. The elementary analysis showed that the atomic ratio of Si tI Al ,.s 2.68 and the copper content was 4.6 wt.%4 This oubstance has the formula, 0.48CuO’0.52Na 200A235.36810 2.2H52 0.
Present substance (2) T wenty-five grams of sodium aluminate containing 26.3 wt.% of Na20, 43,2 wt.% of A1 2 3 and 30.5 wt.» of H20 and 52,4 g of sodium hydroxide containing 77.5 wt.% 12 1 of Na 2 O were dissolved in 612.1 g of distilled water.
This solution was added to 379.9 g of an aqueous sodium silicate solution containing 9.2 wt.% of Na 2
O
and 29.0 wt.% of SiO 2 with stirring. The substance thus obtained has the formula, 12.5Na 2 O-A1 2 0 3 *17.3SiO .454.5H 2 0.
Then, the reactor was closed tightly, the substance charged therein was stirred at 100°C for 48 hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 Lo about 9 and dried at 120°C for 16 hours.
Next, copper ion exchange was carried out in the same manner as in the preparation of the present substance The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to phillipsite group. The elementary analysis showed that the atomic ratio of Si 1o Al was 1.91 and the copper content was 3.8 wt.s.. The electron microscopic measurement showed that the average par-ticle diameter was 2.0 tm. This substance has the formula, 0.32CUO.0.68Na 2 O-Al 2 0 3 *3.82SiO 2 .7.79H 2 0.
Present substance (3) Fifteen grams of sodium aluminate containing 26.3 wt.% of Na 2 0, 43.2 wt.% of Al 2 0 3 and 30.5 wt.% of
H
2 0 and 65.74 g of sodium hydroxide containing 77.5 wt.q of Na 2 O were dissolved in 519.09 g of distilled water.
13 _1 II 1 To this solution were added 107.49 g of SiO 2 (Aerosil) with stirring. The substance thus obtained has the formula, 13.9Na O-Al 2 0 3 -28.2SiO 2 470.9H 2 0.
Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100°C for 24 hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120 0 C for 16 hours.
Next, copper ion exchange was carried out in the same manner as in the preparation of the present substance S 15 The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to phillipsite group. The elementary analysis showed that the atomic ratio of Si to Al was 2.39 and the copper content was 3.2 This substance has the formula, 0.32CuO-0.68Na 2 0.Al 2 0 3 4.78SiO 2 9.48 2 0.
Present substance (4) Fifteen grams of sodium aluminate containing 26.3 wt.% of Na 2 0 43.2 wt.% of A1 2 0 3 and 30.5 wt.% of
H
2 0 and 63.85 g of sodium hydroxide containing 77.5 wt.% of Na20 were dissolved in 276.04 g of distilled water.
This solution was added to 352.43 g of an aqueous colloidal silica sol containing 0.4 wt.% of Na20 and 14 t- Lj 1 30.5 wt.% of SiO 2 with stirring. The substance thus obtained has the formula, 13.9Na20-A1 2 03 28.2SiO 2 470.9H 2 0.
Then, the reactor was closed tightly, the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100 0 °C for 24 hours.
Thereafter, the temperature was lowered again to room temperature, the stirring was carried out at 100°C for another 48 hours.
Next, precipitated powdery crystals were collected by filtration unde’c reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120 0 C for 16 hours.
Thereafter, copper ion exchange was carried 15 out in the same manner as in the preparation of the present substance (1) The X-ray diffractometry demonstrated that the powdery .substance thus obtained was crystalline zeolite 0 f belonging to phillipsite group. The elementary analysis showed that the atomic ratio of Si to Al was o Qe o’a .2.59 and the copper content was 3.4 This substance has the formula, 0.35CuO’0.65Na 2
OAI
2 0 3 5.18Si 0 2 ^o»o .79H20.
Present substance Fifteen grams of sodium alumina-e containing 26.3 wt.% of Na 2 0, 43.2 wt.% of A1 2 0 3 and 30.5 wt.% of and 63.85 g of sodium hydroxide containing 77.5 wt,% 15 ti 1 of Na20 were dissolved in 276.04 g of distilled water.
This solution was added to 352.43 g of an aqueous colloidal silica sol containing 0.4 wt.% of Na20 and 30.5 wt.% of SiO 2 with stirring. The substance thus obtained has the formula, 13.9Na 2 0-Al 2 0 3 -28.2SiO2 470.9H 2 0.
Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100 0 C for 18 hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120°C for 16 hours.
Next, copper ion exchange was carried out in the same manner as in the preparation of the present substance The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to faujasite group. The elementary analysis showed that the atomic ratio of Si to Al was 2.58 and 20 the copper content was 4.7 wt.% This substance has the formula, 0.48CuO-0.52Na 2 0-Al 2 03*5.16SiO 2 .8.93H 2 0.
Present substance (6) Fifteen grams of sodium aluminate containing 26.3 wt.% of Na20, 43.2 wt.% of Al 2 0 3 and 30.5 wt.% of
H
2 0 and 141.63 g of sodium hydroxide containing 77.5 wt.% of Na20 were dissolved in 68.09 g of distilled water. This solution was added to 128.73 g of an 0r 0 0 0 1 0o I 0i 0 16 -s I i ,i r i- 1 aqueous colloidal silica sol containing 0.4 wt.% of and 30.5 wt.% of SiO 2 with stirring. The substance thus obtained has the formula, 29.0Na 2 0-Al 2 0 3 10.3Si0 2 126.2H20.
Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100°C for 130 hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120 0 C for 16 hours.
Next, copper ion exchange was carried out in the same manner as in the preparation of the present substance «a 15 The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to faujasite group. The elementary analysis showed that the atomic ratio of Si to Al was 2.76 and the copper content was 5.4 This substance has the formula, 0.57CuO-0.43Na 2 0O*Al 2 0 3 5,52SiO 2 8.87H 2 0.
0 0 0 0 Present substance (7) SFifteen grams of sodium aluminate containing 26.3 wt.% of Na 2 0, 43.2 wt.% of A1 2 0 3 and 30.5 wt.% of H 20 and 63.85 g of sodium hydroxide containing 77.5 wt.% of Na20 were dissolved in 276.04 g of distilled water.
This solution was added to 352.43 g of an aqueous colloidal silica sol containing 0.4 wt.% of Na20 and c* 17 -11- V uuv mcaly ac J_ %J LJUJW:.
Its dosage rate can be reduced because the phytotoxicity to crops can be markedly improved. It can 4 4 Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100 0 C for hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120’C for 16 hours.
Next, copper ion exchange was carried out in the same manner as in the preparation of the present substance Co The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to faujasite group. The elementary analysis showed that the atomic ratio of Si to Al was 2.35 and the copper content was 5.1 The electron microscopic measuredeht showed that the average particle diameter was 1.0 pm. This substance has the formula, 0.48Cu0O0.52Na 2 Al2 0 3 .’470SiO 2 8.5H2 0.
Present substance (8) Crystalline zeolite before the copper ion exchange was obtained in the same manner as in the preparation of the present substance Then, 2070 ml of a 0.3 M aqueous copper sulfate solution was added to 90 g of zeolite thus obtained, the pH of the system was adjusted to 4.2 with 10% sulfuric acid and ion 18 I’ iiii -1 r- ~rrr~m 1 exchange was carried out with stirring at 70 0 C for 4 hours. After the ion exchange had been completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water until copper ions and sulfate radicals were not detectable and dried at 120 0 C for 16 hours.
The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to faujasite group. The elementary analysis showed that the atomic ratio of Si to Al was 2.58 and the copper content was 7.8 The electron microscopic measurement showed that the average o particle diameter was 1.5 pm. This substance has the formula, 0.78CuO-0.22Na20-Al203 5,16SiO2 8.09H 26 3, 0 0 Present substance (9) Fifteer grams of sodium aluminate containing 26.3 wt.% of Na20, 43.2 wt.% of Al 2 0 3 and 30.5 wt.% oo of H 0 and 63.85 g of sodium hydroxide containing 77.5 wt.% of Na20 were dissolved in 276.04 g of distilled water. This solution was added to 352.43 g of an aqueous colloidal silica sol containing 0.4 wt.% c, of Na 0 and 30.5 wt.% of SiO 2 with stirring. The a on substance thus obtained has the formula, 13.9Na 2
O-A
2 0 3 2 8.2SiO 2 470.9H 2 0.
Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 80OC for 168 hours.
19 I ;j puivLpp.Le Ufnytophthora cinnamomi), late blight of potato, tomato and eggplant (Phytophthora infestans) late blight of tobacco, broad bean and Welsh onion (Phytophthora 6 4 1 Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 Kto about 9 and dried at 120’C for 16 hours.
Next, to 5 g of these crystals were added 100 ml of a 0.048 M aqueous copper sulfate solution, the pH of the system was adjusted to 4.2 with hydrochloric acid and ion exchange was carried out with stirring at 75’C for 4 hours. Afte t.he ion exchange had been completed, the reaction solution was filtered, i and the resulting crystals were washed with distilled water until copper ions and sulfate radicals were not detectable and dried at 1201C for 16 hours.
1 The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to faujasite group. The elementary I analysis showed that the atomic raiio of Si to Al was 2.47 and the copper content was 7.0 Electron microscopic measurement showed that the average particle diameter was 0.5 pm. This substance has the formula, S. 0.68CuO0.32Na 2 O.A 2 0 3 .4.94SiO8.02H0.
fil0tatiof und ereucessolvssure,2washedgwit distilled
I
toesent substance Fifteen grams of sodium aluminate containing 26.3 wt.% of Na 2 0, 43.2 wt.% of A1 2 0 3 and 30.5 wt.% of
H
2 0f 20.89 g of sodium hydroxide containing 77.5 wt.% of Na 2 o and 09.71 g of potassium hydroxide containing 84.0 wt.% of K 2 0 were dissolved in 266.42 g of distill 20 1 water. This solution was added to 354.53 g of an aqueous colloidal silica sol containing 0.4 wt.% of Na20 and 30.5 wt.% of SiO2. The substance thus obtained has the formula, 5.6K 2 0-5.5Na2O-Al 20328.5SiO 2 463H 2 0.
Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100°C for 70 hours.
Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120 0 C for 16 hours.
Next, copper ion exchange was carried out in the same manner as in the preparation of the present substance The X-ray diffractometry demonstrated that 0 the powdery substance thus obtained was crystalline zeolite belonging to chabazite group. Also, the elementary analysis showed that the atomic ratio of Si to Al was 3.11 and the copper content was 1.7 wt.%.
20 This substance has the formula, o 0.21CuO.0.35K 0-0.44Na 20Al20. 6.22SiO- 12.53H 0.
Present substance (11) Fifteen grams of sodium aluminate containing 26.3 wt.% of Na 2 0, 43.2 wt.% of A 2 l0 3 and 30.5 wt.% of
H
2 0, 23.53 g of sodium hydroxide containing 77.5 wt.% of Na20 and 14.25 g of potassium hydroxide containing 84.0 wt.% of K20 were dissolved in 179.95 g of distilled 21 i: i i tion, dispersion, wetting, etc. include anionic surface active agents such as the salt of alkyl sulfates, 8 1 water. This solution was added to 244.95 g of an aqueous colloidal silica sol containing 0.4 wt.% of and 30.5 wt.% of SiO 2 The substance thus obtained has the formula, 2.0K 2 0-5.9Na20-A1203 19.6SiO 2 -316H 2
O.
Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100°C for hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120 C for 16 hours.
Next, copper ion exchange was carried out in the same manner as in the preparation of the present substance The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to chabazite group. The elementary analysi showed that the atomic ratio of Si to Al was 3.59 and the copper content was 2.6 This substance S» 20 has the formula, S0.35CuO-0.29K 2 0.0.36Na 2 0-Al 2 0 3 7.18SiO 2 13.20H 2 0.
Reference substance (a) 14.37 Grams of sodium aluminate containing 26.3 wt.% of Na 2 0, 43.2 wt.% of Al 2 0 3 and 30.5 wt.% of
H
2 0 and 14.22 g of sodium hydroxide containing 77.5 wt.% of NaO2 were dissolved in 119.81 g of distilled water. This solution was added to 33.54 g of an aqueous 22 L, 1 colloidal silica sol containing 0.4 wt.% of Na20 and 30.5 wt.% of SiO 2 with stirring. The substance thus obtained has the formula, 4.0Na2 OAl 2 3 2.8SiO2-137.4H 2
Q.
Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100 0 C for hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dtied at 120 0 C for 16 hours.
Next, to 5 g of these crystals were added 118 ml or a 0.04 M aqueous copper sulfate solution, the pH of the system was adjusted to 6.9 with 10% caustic soda and ion exchange was carried out with stirring at room temperature for 4 hours. After the ion exchange had been completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water until copper ions and sulfate radicals were not detectable and dried at 120QC for 16 hours.
The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to faujasite group. The elementary analysis showed that the atomic ratio of Si to Al was 1.43 and the copper content was 5.4 rht.%.
The electron microscopic measurement ;howed that the average particle diameter was 2.0 1im. This substance has the formula, 23 i 10.38Cu0*0.62Na 2 .A1 2 0 3 *2.86Sj0 2 .6.08 2 0 Reference substance (b) A zeolite, a precursor, was obtained in the same manner as in the preparation of the reference substance To 5 g of the zeolite thus obtained were added 60 ml of a 0.16 M aqueous copper sulfate solution, the pH of the system was adjusted to 6.9 with 10% caustic soda and ion eXchange was carried out with stirring at rtoom temperature for 4 hours. After the ion eXchange had been completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water t..til copper ions and sulfate radicals were not detectable and dried at 120 0
C
for 16 hours.
The X-ray diffractomo’try demonstrated that the powdery substance thus ob’.ained was crystalline zeolite belonging9 to f4Mjasite group. The elementary analysis showed that the atomic ratio of Si to Al was 1.43 and the copper content was 9.9 wt.,.
20 The elootroa microscopic measurement showed that -the average particle diameter was 240 p’m, This substance has the formula, 0.70Cu0.0.30Na 2 OA1 2 0 3 2.86SiO 2 .5.52H 2 0.
Referonce substance (c) Fifteen grams of Sodium alUminate containing 26.3 wt.% of NaO, 43.2 wEA of Al 20 3 and 30.5 wt.q% 4 1 of H 2 0 and 21.55 g of soidum hydroxide containing 77.5 wt.% of Na 2 0 were dissolved in 262.93 g of distilled water. This solution was added to 370.66 g of an aqueous sodium silicate solution containing 9.2 wt.% of Na 2
O
and 29.0 wt.% of SiO 2 with stirring. The substance thus obtained has the formula, 13.9Na20 A1 2 0 3 .28.2SiO 2 470.9H 2 0.
Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100°C for 24 hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 1200C for 16 hours, Next, copper ion exchange was carried out in the same manner as in the preparation of the present substance The X-ray diffractometry demonstrated that the powdery substance thus obtained was a non-crystalline aluminosilicate. The elementary analysis showed that the atomic ratio of Si to Al was 3.04 and the copper content was 4.7 This substance has the formula, 0,53Cu0″0.47Na 2 0*Al20 3 6.08SiO 2 *9.92HgO.
Reference substance (d) A zeolite, a precursor, was obtaine’. in the same manner as in the preparation of the reference substance To 5 of the zeolite thus obtained 2S 1 were added 100 ml of a 0.048 M aqueous copper sulfate solution, the pH of the system was adjusted to 4.2 with hydrochloric acid and ion exchange was carried out with stirring at 75QC for 4 hours. After the ion exchange had been completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water Until copper ions and sulfate radicals were not detectable and dried at 120 0 C for 16 hours.
The X-ray diffractometry demonstrated that the powdery substance thus obtained was a non-crystalline aluminosilicate, The elementary analysis showed that the atomic ratio of Si to Al was 1.43 and the copper content was 5.5 wt.%d The electron microscopic measurement showed that the average particle diameter was 2.0 pm, This substance has the formula, 0 39Cu0 0. 6l1NaO *A1 2 0 3 2 .86SiQ* 5. 94H 0Q Reference substance (e) 35.4 Grams of sodium aluminate containing 262a wtA% of Na 2 0, 43,2 wt.0 of A1 2 0 3 and 30.5 wto of HQ and 29.89 g of sodium hydroxide containing 77.5 wtLG of Na 2 O were dissolved in 194.2 g of distilled water. This solution was added 6P.07 g of an aqueous sodium silicate solution containing 9.2 wt.% of Wa 2
O
and 29.0 wt.o of Si 2 with stirring. The substance thus obtained has the formula, 4. Na20 ‘A 2 3 2. s08o 2 02.U2 ’21 -26 1;CI._1-.i-l-Lii i -iilii I 1 Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 3 hours and then at 60 0 C for 3 hours.
Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH o. the washings became from about 8 to about 9 and dried at 120°C for 16 hours.
Ne>t, to 5 g of these crystals were added ml of a 0.16 M aqueous copper nitrate solution, the pH of the system was adjusted to 6.9 with 10% caustic soda and ion exchange was carried out with stirring at room tempexrture for 4 hours. After the ion exchange o had been completed, the reaction solution was filtered, and the resulting crystals wer washed with distilled water until copper ions and sulfate radicals were not detectable and dried at 120°C for 16 hours.
The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to faujasite group. The elementary analysis showed that the atomic ratio of Si to Al was 1.15 and the copper content was 10 wt.%.
The electron microscopic measurement showed that the average particle diameter was 1.8 pm. This substance has the formula, 0.63CuO.0.37Na 2 0.A 0 3 .2.30SiO 2 .91H20.
Reference substance (f) A zeolite, a precursor, was obtained in the 27 i I r- 1 same manner as in the preparation of the reference substance To 5 g of the zeolite thus obtained were added 100 ml of a 0.048 M aqueous copper sulfate solution, the pH of the system was adjusted to 4.2 with hydrochloric acid and ion exchange was carried out with stirring at 75°C for 4 hours. After the ion exchange had been completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water until copper ions and sulfate radicals were not detectable and dried at 120°C for 16 hours.
The X-ray diffractometry demonstrated that the powdery substance thus obtained was a non-crystalline aluminosilicate. The elementary analysis showed that the atomic ratio of Si to Al was 1.15 and the copper content was 5.7 The electron microscopic measurement showed that the average particle diameter was 1.8 pm. This substance has the formula, 0,36Cu00..64Na 2 0 Al 2 C 3 .2.30Si 2 5.26H 2 0.
Reference substance (g) 20 Fifteen grams of sodium aluminate containing 26,3 wt.% of Na20, 43.2 wt.% of Al 0 3 and 30.5 wt.% ,O of H 2 0 and 58.48 g of sodium hydroxide containing 77.5 wt.% of Na20 were dissolved in 374.33 g of distilled water. This solution was added to 249.84 g of an aqueous colloidal silica sol containing 0.4 wt.% of Na 2 0 and 30.5 wt.% of SiO 2 with stirring. The substance thus obtained has the formula, 12.2Na20-Al 2 0 3 20.
0 SiO 2 496H20.
28
/I
1 Then, the reactor was closed tightly, and the substance charged therein was stirred firstly at room temperature for 24 hours and then at 100 0 C for 24 hours. Precipitated powdery crystals were collected by filtration under reduced pressure, washed with distilled water until the pH of the washings became from about 8 to about 9 and dried at 120 0 C for 16 hours.
Next, to 5 g of these crystals were added 118 ml of a 0.5 M aqueous copper sulfate solution, the pH of the system was adjusted to 4.2 with 10% sulfuric acid and ion exchange was carried out with stirring at 70 0 C for 4 hours. After the ion exchange had been completed, the reaction solution was filtered, and the resulting crystals were washed with distilled water until copper ions and sulfate radicals were not detectable and dried at 120 0 C for 16 hours. The X-ray diffractometry demonstrated that the powdery substance thus obtained was crystalline zeolite belonging to analcime group. The elementary analysis showed that a’ 20 the atomic ratio of Si to Al was 2.41 and the copper content was 2.0 This substance has the formula, 0.20CuO 0.80Na20 A1 2 0 3 4. 82SiO 2 .10.17H 2 0.
060 Reference substances and (m) A zeolite, a precursor, was obtained in the same manner as in the preparation of the present substance This substance was ton-exchanged with each of zinc, tin, iron, nickel, magnesium and cobalt 29 _.li 1 according to the foregoing method for ion-exchanging with copper ion. The amount of each metal to be added to 5 g of the above zeolite powder was as follows: ml of a 0.16 M aqueous zinc nitrate solution for zinc ion, 30 ml of a 0.08 M aqueous stannic chloride solution for tin ion, 30 ml of a 0.18 M aqueous ferric chloride solution for iron ion, 100 ml of a 0.05 M aqueous nickel nitrate solution for nickel ion, 100 ml of a 0.12 M aqueous magnesium nitrate solution for magnesium ion, and 100 ml of a 0.04 M aqueous cobalt nitrate solution for cobalt ion. After each solution had been added to 5 g of zeolite, the pH of the system Sr was adjusted to 4.2 with a 10% aqueous caustic soda solution, and the stirring was carried out at 700C for Si 15 4 hours. After the ion exchange had been completed, the zeolite powder was filtered off, washed with 200 ml of distilled water and dried at 120°C for 16 h.,urs.
The X-ray diffractometry demonstrated that the resulting each powder was crystalline zeolite belonging to faujasite group. The elementary analysis showed that the atomic ratio Of Si to Al of each powder was 2.58.
The following table shows the metal content and composition of each substance thus obtained.
30 Test Name of metal used conetCmosto substance for ion exchange contenomoito Zinc (Zn 2+ 5.6 O.55ZnO-O.45Na 2 O-A 2 0 3 .5.16 Sio 2 98H Tin (Sn 4 5.3 O.28Sn0O .44Na 2 OAl 2 0 3 2 22H 2 0 Iron (Fe 3 7.2 0.33Fe 2 0 3 ‘O.lNa 2 O-A1 2 0 3 5.16Si0 2 84H 2 0 (kc) Nickel (Ni 2) 5.4 O.59NiO-O.4lNa 2 0A1 2 0;3 15-l6SiO 2 ‘9-16H 2 0 Magnesium (Mg 2 2.5 O.62MgO0O.38Na 2 O- A 2 0 3 5.l6SiO 2’7.64H (in) Cobalt (Co 2) 4.7 0.5OCoO-0.5ONa 2 O -A1 2 0 3 5.l6Si 2 .8.43 I ~ii ii 1 In the following examples, the controlling activity was evaluated in six grades described below, 4, 3, 2, 1, 0, according to the condition of disease of test plants at the time of examination, i.e.
The degrees of colony and infected area on the leaves, stems, etc. observed with the naked eyes.
Neither colony nor infected area is observed.
4 About 10% of colony or infected area is observed.
3 About 30% of colony or infected area is observed.
2 About 50% of colony or infected area is observed.
1 About 70% of colony or infected area is observed.
0 More than about 70% of colony or infected area is observed, there being no difference in the condition of disease between the treated S 15 and untreated plots.
Example 1 Controlling test on downy mildew of cucumber (Pseudoperonospora cubensis) (preventive effect) Sandy loam was filled in plastic pots, and cucumber was sowed and cultivated into seedlings in the second true leaf stage for 20 days in a greenhouse.
Th^ wettable powder of each test substance prepared according to Formulation example 1 was diluted with water to a prescribed concentration and foliar-applied onto the seedlings so that the spray liquor was thoroughly attached to the leaf surface. After spraying, the seedlings were inoculated by spraying the spore suspension 32 I 1., I, -i–r-utu ~iill~;’ I~; i D i) 7 ii s C9 o 1 of Pseudoperonospora cubensis. After inoculation, the seedlings were cultivated firstly at 20 0 C under a highly humid condition for 1 day, and then under lighting for 5 days to examine the controlling activity. The results are shown in Table 1.
Table 1 Test substance Application Copper Controlling Subsance concentration concentration activity No. (ppm) 0,260 (120) 4 (1) 0.065 30) 4 0.316 (120) 4 (2) 0.079 30) 4 0.375 (120) 4 (3) 0.094 30) 3 0.353 (120) 4 (4) 0.088 30) 3 0.255 (120) 4 0.064 30) 3 0.222 (120) 4 (6) 0.056 30) 3 0.235 (120) 4 (7) 0.059 30) 3 0 0 0 o 0 0.154 0.038 (120) 30) 4 cont’d. 1- 33 Table 1 (Cont’d.) Test substance Sbtne Application Copper Cnrl Sbtneconcentration concentration) activit No. (ppm) 2 0.152 (120) (9) 0.038 (30) 4 0.706 (120) 4 0.176 (30) 3 0,462 (120) 4 0.115 (30) 3 ()0.222 (120) 3 0.056 C30) 0 0.121 (120) 3 (b) 0.030 C30) 1 ()0.255 (120) 3 0.064 C30) 2 0.190 (120) 3 0.048 C30) 1 0.120 (120) 2 0.030 C30) 0 0.053 (30) 0 ()0.600 (120) 0 0.150 (30) 0 ()0.214 (1.20) 1 0.054 C30) 0 -cont’d. 34 Table 1 (Contdc.) 0 0 Test substance Sbtne Application Copper c tring Subsanceconcentration concentration) atvy Mo (ppm) 0.226 (120) 0 Wi 0.057 (30) 0 0.167 (120) 0 (j) 0.042 C3Q) 0 0.222 (120) 2 (k) 0.056 (30) 0 0.480 (120) 0 0.120 (30) Q 0.255 (120) IL 0.064 (30) 0 (A)*1(120) 0 0 2(120)0 30)0 Basic copper chloride (same applies hereinafter).
*2 Bordeaux mixtur~e (mixture oE copper sulfate and qjuick lime) (same applies herzeinafter).
35 iii r*~i- 1 Example 2 Controlling test on late blight of tomato (Phytophthora infestans) (preventive effect) Sandy loam was filled in plastic pots, and tomato (var., Ponteroza) was sowed and cultivatea into seedlings in the second to third true leaf stage for 20 days in a greenhouse. The wettable powder of each test substance prepared according to Formulation example 1 was diluted with water to a prescribed concentration and foliar-applied onto the seedlings so that the spray liquor was thoroughly attached to the leaf surface. After spraying, the seedlings were inoculated by spraying the spore suspension of SPhytophthora infestans. After the inoculation, the seedlings were cultivated firstly at 20°C under a highly humid condition for 1 day, and then under lighting for 5 days to examine the controlling activity.
The results are shown in Table 2.
Table 2 Test substance Substance Application Copper ontrolling No. concentration concentration activity (ppm) 0.260 (120) (1) 0.065 30) 0.316 (120) (2) 0.079 30) 4 cont’d. 36 Table 2 (Cont’d.) Test substance Subtace Application (Copper Controlling Sbtne concentration concentration activity No. W% (c (ppm) 0.375 (120) (3) 0.094 (30) 0.353 (120) (4) 0.088 (30) 3 0.255 (120) 0.064 (30) 3 0.222 (120) (6) 0.056 (30) 3 0.235 (120) (7) 0.059 (3Q) 0.154 (120) 0.038 (30) 3 0.706 (120) 0.176 (30) 4 0.462 (120) U.115 (30) 0.222 (120) 3 (a) 00630) 1 0b)121 (120) 3 0. 030 (30) 1 0.255 (120) 2 0.064 (30) 0 C(cnt’d.
37 Table 2 (Coqtfd.) Test substance Substance No.
Application concentration
M%
(Cpper Koncen t ra t ion2 Contraolling activity 0.120 (120) 2 (e) 0.030 (30) 0 0.211 (120) 0 Mf 0.053 (30) 0 0.600 (g) 0.150 (30) 0 0.214 (120) 0 (h) 0.054 (30) 0 Q. 226 (120)Q 0,057 (30) 0 0.167 (120) 0 Q0042 (30) 0 0 .2’22 (120)0 0.056 (30) 0 0. 480Q (120) 0 0.120 0) 0 0.255 (120) 0 0.064 (30) 0 0 0 (120)0 0 38 1 Example 3 Controlling test on alternaria spot of Japanese radish (preventive effect) Sandy loam was filled in plastic pots, and Japanese radish (var., 60-nichi daikon) was sowed and cultivated into seedlings in the cotyledortous stage for 6 days in a greenhouse. The wettable powder of each test substance prepared according to Formulation example 1 was diluted with water to a prescribed concentration and foliar-applied onto the seedlings so that the spray liquor was thoroughly attached to the leaf surface.
After spraying, the seedlings were inoculated by spraying the spore suspension of the fungi of alternaria spot of Japanese radish. After inoculation, the i seedlings were cultivated firstly at 18 0 C under a highly humid condition for 1 day, and then undor lighting for 3 days to examine the controlling ctivity.
The results are shown in Table 3.
39 ly- Table 3 c Subs tance No.
Test subs3teaiCE? Appi ca tion Copper concr. ,tration Koncentration) (ppm) 0.1174 (120) 0,038 Controlling activity 0.152 (120) 4 (9) 0.036 30) 3 0.121 (120) A (b) 0.C3 30) 1 (120) 3
(A)
0 -(120) 4
(D)
0 1 4xample 4 Controllin -test on angular leaf spot of cucumber (Pseudomonazs lachrymatis) (residual effect test) Sandy loam was filled in plastic potst and cucumber (var., Sigam-hanjiro) was sowed and cultivatod into seedlings for 35 days in a greenhouse.
The wettable powder of each test substance prepared according -to Vormulation example 1 was dliluted with water to a prescribed concentration. and foiIr-applbied onto the seedlings so that the spray liquor Was thoroughly attached to the loaf surface. After sprayingo the 40 ix 1 1 seedlings were cultivated for 7 days in a greenhouse in the daytime and 17″C in the night) and inocula–d by spraying the spore suspension of Pseudomonas lachrymans,. After inoculation, the seedlings were cultivated firstly under a highly humid condition for about 24 hours, and then under the above gre ihouse conditior for 10 days to examine the controlling activity. The results are shown in Table 4.
Table 4 Test substance Substance Application Copper Contoling No concentration concentration) a vy (ppm) 0.260 (120) 4 .1) 0,065 30) 4 0.375 (120) 4 (3) 0.094 30) 4 0.222 (120) 4 (6) 0.056 30) 4 0,154 (120) 4 (8) 0,038 30) 4 0.462 (120) 4 (11) 0.115 30) 4 Cont’d. 41 -C Table 4 (Cont’d.) Test substance Substance Application Copper Controlling o concentration concentration activity (ppm) 0.121 (120) 3 (b) 0.030 30) 2 0.190 (120) 3 (d) 0.048 30) 1 0.120 (120) 3 (e) 0.030 30) 0 0.211 (120) 2 0.053 30) 0 (120) 0
(A)
30) 0 1 Example 5 Controlling test on bacterial grain rot of rice (Pseu(t)monas crLumae) (preventive effect) Sandy loam was filled in plastic pots, and rice (var., Kinki No. 33) was sowed and cultivated into seedlings for 70 days in a greenhouse. The wettable powder of each test substance prepared according to Formulation example 2 was diluted with water to a prescribed concentration and sprayed so that the spray liquor was thoroughly attached to the ears. After spraying, the seedlings were air-dried and inoculated by spraying the spore suspension of Pseudomonas glumae.
42 i i 1 After inoculation, the seedlings were cultivated firstly at 23°C under a dark and highly humid condition for 1 day, and then under a greenhouse condition (27C) for 9 days to examine the controlling activity.
The results are shown in Table Table Test substance Substance Application Copper Controlling No. concentration concentration (ppm) 0.520 4 0.750 (240) 4 0.4,.4 (240) 4 0.308 (240) 4 (11) 0.924 40) 4 0.242 (240) 1 0.380 (240) 1 0,240 (240) 0 0.422 (240) 0 (240) 0 43 1 Example 6 Controlling test on anthracnose of cucumber (Colletotrichum lagenarium) (preventive effect) Sandy loam was filled in plastic pots, and cucumber (var., Sagami-hanjiro) was sowed and cultivated into seedlings in the cotyledonous stage for 14 days in a greenhouse. The wettable powder of each test substance prepared according to Formulation example 1 was diluted with water to a prescribed concentration and foliar-applied onto the seedlings so that the spray liquor was thoroughly attached to the leaf surface.
3 After spraying, the seedlings were inoculated by spraying the spore suspension of Colletotrichum lagenarium. After inoculation, the seedlings were cultivated firstly at 23°C under a highly hunid condition for 1 day, and then under lighting for 4 days to examine the controlling activity. The results are shown in Table 6.
44 L, Table 6 Test substance Application Copper Controlling Substance concentration concentration) activity No. M~ Kc (ppm) 0.260 (120) 4 (1) 0.065 (30) 3 0.353 (120) 4 (4) 0.088 (30) 1 0.222 (120) 4 (6) 0.056 (30) 2 0.154 (120) 4 0.0.38 (3Q) 4 0.152 (120) 4 (9) 0.038 (30) 4 0.706 (120) 4 0.176 (30) 2 0.121 (120) 2 (b) 0.030 (30) 0 0.255 (120) 3 (c) 0.064 (30) 0 0.120 (120) 1 0.030 (30) 0 0.211 (120) 0 0.053 (30) 0 0.600 (120) 0 (g) 0.150 (30) 0 -Cont’d. 45 I- pi Table 6 (Cont’d.) Test substance Controlling Se Application Copper Cntroling Substance concentration concentration activity No. (ppm) (120) 0
(A)
0 (120) 0 4 I 46

Claims (4)

1. An agricultural and horticultural fungicidal composition consisting essentially of a fungicidally effective amount of at least one zeolite selected from the group consisting of faujasite group and phillipsite group represented by the formula, aCuC 20 -A12 0 3 bSiO 2*cH20 wherein M represents a sodium and/or potassium atom, and a, b and c fall in the following ranges, 0 0 0 o 0 a 1, 3 b 12, 0 c 0 09 0 0 So together with an inert carrier. 0 6 0 a

2. An agricultural and horticultural fungicidal 0oo 0 composition according to Claim 1, consisting essentially of a fungicidally effective amount of at least one zeolite selected from the group consisting of faujasite group and phillipsite group represented by the formula, aCuO *(l-a)M 2 0 Al 2 0 3 bSi02.cH20 wherein M represents a sodium and/or potassium a~om, and o a, b and c fall in the following ranges, 0 0 a 3.5 b 8 c a 1, 3.5< b 8, 0 c together with an inert carrier. I, .1 48 3. A method for controlling plant pathogenic fungi which comprises applying a fungicidally effective amount of at least one crystalline zeolite selected from the group consisting of faujasite group, chabazite group and phillipsite group represented by the formula, 2 0 3 bSiO 2 wherein M represents a sodium and/or potassium atom, and a, b and c fall in the following ranges, 0 a 1, 3 b 12, 0 c a a Sto plant pathogenic fungi. a a 4. A method for controlling plant pathogenic fungi 4 0 according to Claim 3, which comprises applying a fungicidally effective amount of at least one crystalline zeolite selected from the group consisting of faujasite 0on group and phillipsite group represented by the formula, *000 aCuO*(l-a)M 2 0.Al 2 3 bSiO 2 .cH 2 0 a o S wherein M represents a sodium and/or potassium atom, an' o a a, b and c fall in the following ranges, 0 0 a 1, 3.5 b 0< c to plant pathogenic fungi. iil7C L-~ 49 An agricultural and horticultural fungicidal composition consisting essentially of a fungicidally effective amount of at least one zeolite selected from the group consisting of faujasite group and phillipsite group represented by the formula, aCuO.(l.a)M 2 0 -Al 2 0 3 bSiO 2 .cH 20 wherein M represents a sodium and/or potassium atom, and a, b and c fall in the following ranges, 4 s 0 a 1, 3 b 12, 0 c and an inert carrier selected from the group consisting of kaoline clay, attapulgite clay, bentonite, terra alba, pyrophillite, talc, diatomaceous earth, calcite, corn stalk powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon dioxide, calcium lignosulfonate, sodium lauryl sulfate, polyoxyethylene sorbitan monooleate, CMC and water. V DATED THIS 5TH DAY OF DECEMBER 1990 SUMITOMO CHEMICAL COMPANY, LIMITED SBy its Patent Attorneys GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia. AU20547/88A 1987-09-04 1988-08-09 A copper zeolite fungicide composition Ceased AU608038B2 (en) Applications Claiming Priority (2) Application Number Priority Date Filing Date Title JP22229387 1987-09-04 JP62-222293 1987-09-04 Publications (2) Publication Number Publication Date AU2054788A AU2054788A (en) 1989-03-09 AU608038B2 true AU608038B2 (en) 1991-03-21 Family ID=16780096 Family Applications (1) Application Number Title Priority Date Filing Date AU20547/88A Ceased AU608038B2 (en) 1987-09-04 1988-08-09 A copper zeolite fungicide composition Country Status (9) Country Link US (1) US4986989A (en) EP (1) EP0306035A3 (en) AU (1) AU608038B2 (en) BR (1) BR8804526A (en) ES (1) ES2011851A6 (en) FR (1) FR2619991B1 (en) GB (1) GB2209469B (en) GR (1) GR1000337B (en) IT (1) IT1224721B (en) Families Citing this family (20) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title CA2044893C (en) * 1990-06-20 1998-11-03 Senshi Kasahara Transition metal-containing zeolite having high hydrothermal stability, production method thereof and method of using same US6531093B1 (en) * 1998-12-24 2003-03-11 Hiromi Houzawa Germicidal ceramics, method for producing the same, and sterilizing method using the same US6582229B1 (en) * 2000-04-25 2003-06-24 Align Technology, Inc. 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Antibacteria property Also Published As Publication number Publication date US4986989A (en) 1991-01-22 ES2011851A6 (en) 1990-02-16 GR880100570A (en) 1989-06-22 EP0306035A3 (en) 1990-06-13 IT1224721B (en) 1990-10-18 GB8820587D0 (en) 1988-09-28 GB2209469A (en) 1989-05-17 IT8848304D0 (en) 1988-08-26 BR8804526A (en) 1989-04-04 GB2209469B (en) 1992-01-02 AU2054788A (en) 1989-03-09 FR2619991B1 (en) 1991-11-15 GR1000337B (en) 1992-06-25 EP0306035A2 (en) 1989-03-08 FR2619991A1 (en) 1989-03-10 Similar Documents Publication Publication Date Title AU608038B2 (en) 1991-03-21 A copper zeolite fungicide composition US6689392B2 (en) 2004-02-10 Methods and compositions for controlling plant pathogen KR20180038556A (en) 2018-04-16 Bacterial strains and uses thereof for controlling plant diseases AU2002228315A1 (en) 2003-02-20 Methods and compositions for controlling plant pathogen CA2877981A1 (en) 2014-01-09 Agricultural compositions and applications utilizing mineral compounds US5183477A (en) 1993-02-02 Foliar spray agent for protecting agricultural and horticultural plants against disease injury RU2037485C1 (en) 1995-06-19 Arylpyrrole derivatives and method of their synthesis CN112204038A (en) 2021-01-08 Agricultural bactericide and application and preparation method thereof CS262428B2 (en) 1989-03-14 Fungicide for utilization in agriculture and method of its efficient component production SU708978A3 (en) 1980-01-05 Fungicidic-bactericidic agent JP4630434B2 (en) 2011-02-09 Agricultural / horticultural suspension in water US4264593A (en) 1981-04-28 Tris(aryl)alkyl phosphonium halides and pesticidal compositions thereof HU209046B (en) 1994-03-28 Antifungal compositions and process for the production thereof RO122830B1 (en) 2010-03-30 Fungicidal composition based on salts of the n,n-ethylene-bis-thiocarbamic acid and process for preparing the same JPH01156905A (en) 1989-06-20 Fungicide for agricultural and horticultural use EP2987409B1 (en) 2018-10-24 Plant protection agent and method for controlling plant disease JP2003267810A (en) 2003-09-25 Disinfecting and mineral-replenishing agent for agriculture and method for producing the same US4058600A (en) 1977-11-15 Fungicidal treatment and composition EP3994112A1 (en) 2022-05-11 Plant nutrient compositions of transition metal phosphate and combinations thereof JPS5949203B2 (en) 1984-12-01 Fungicide JPS59186908A (en) 1984-10-23 Agricultural and horticultural fungicide CA1118776A (en) 1982-02-23 Bis(dithiocarbamate)salts GB2143736A (en) 1985-02-20 Fungicidal composition GB1560312A (en) 1980-02-06 Agricultural and horticultural fungicidal composions US3705241A (en) 1972-12-05 Fungicidal process employing organic phosphorous acid esters
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