CA1334823C - Coated agricultural chemicals - Google Patents
Coated agricultural chemicalsInfo
- Publication number
- CA1334823C CA1334823C CA000585401A CA585401A CA1334823C CA 1334823 C CA1334823 C CA 1334823C CA 000585401 A CA000585401 A CA 000585401A CA 585401 A CA585401 A CA 585401A CA 1334823 C CA1334823 C CA 1334823C
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- Prior art keywords
- coated
- acid
- agricultural chemical
- formulation
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Classifications
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
Abstract
A coated agricultural chemical comprises a powdery effective component of an agricultural chemical coated with at least one member selected from the group consisting of esters of aliphatic acids and aliphatic polyols and phospholipids in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the effective component. The agricultural chemicals exhibit high efficiency even at a concentration lower than that conventionally used and low phytotoxicity to plants.
Description
SPECIFICATION
TITLE OF THE lNV~:N ~ lON
Coated Agricultural Chemicals RACRG~OUND OF THE lNv~NTlON
Field of the Invention - The present invent~on relates to coated agricultural -chemicals or formulations which can exhibit s~fficiently-high efficiency even at a concentration lower than that of conventionally used.
Description of the Prior Art Hitherto, there have widely been used such heavy metal compounds as cupreous agents, mercurials and arsenicals;
organochlorine agricultural chemicals and organophosphorus agricultural chemicals as formulations of agricultural chemicals. However, all of these agricultural chemicals are not only harmful to human body and animals but also contaminate the soil which leads to enviloru..ental pollution developed into a severe social problem accompanied by the use of effective amount thereof.
Under such circumstances, Japanese Patent Publication for Opposition Purpose (hereunder referred to as "J.P.
ROKOKU") No. 57-48525 teaches that a fungicide mainly .~
composed of an ester of an aliphatic polyol and an aliphatic acid and sodium hydrogen carbonate shows a prevention effect on various blight of plants and those observed during storing fruits and is highly safe with respect to human body, ~ni~=ls and plants.
However, the agricultural chemicals prepared according to such a method must be used in a high concentration in order to achieve a desired efficiency when they are used in an amount comparable to that-of the conventional ones and on the contrary, if the concentration thereof is limited to a low level, a desired efficiency is attained only when they are used in a large amount.
To eliminate such disadvantages, the inventors of this invention developed a formulation of agricultural chemicals (see Japanese Patent Unexamined Published Application (hereunder referred to as "J.P. KOKAI") No. 63-233902).
However, such a formulation is not still satisfied since it provides a desired effect only when the concentration of the effective component is relatively high, and when the state of blight occurrence is severe, its effect becomes low.
SUMMARY OF THE lNv~NllON
Accordingly, an object of the present invention is to provide coated agricultural chemicals or formulations which exhibit high efficiency even at a low concentration.
The aforementioned object of the present invention can be achieved by providing a coated agricultural chemical which comprises a powdery effective component of an agricultural chemical coated with at least one member selected from the group consisting of aliphatic acid esters of aliphatic polyols and phospholipids in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the effective component.
BRIEF EXPLANATION OF THE DRAWINGS
The present invention will hereunder be explained in more detail with reference to the accompanied drawings, wherein:
Fig. 1 shows the prevention value of various agricultural formulations for black spot disease of oranges, plotted against the concentration of the formulation;
Fig. 2 shows the relation between the prevention value of various agricultural formulations and the forms thereof while taking the number of spots due to disease into consideration and changing the concentration of the formulations;
Fig. 3 shows the relation between the prevention value of various formulations with respect to mildew of cucumber and the concentration thereof, observed when the state of disease is medium (the number of spots due to disease: 200/leaf);
-Fig. 4 shows the relation between the prevention value of various agricultural formulations for mildew of cucumber and the forms thereof while taking the state of the disease into consideration;
Fig. 5 shows the relation between the prevention value of various agricultural formulations and the concentration thereof observed when the state of disease is severe; and Fig. 6 is attached hereto to demonstrate the degree of - phytotoxicity of the coated NaHCO3 formulation, NaHCO3 formulation and an aqueous solution of non-coated NaHCO3 and shows the relation between the number of spots due to agricultural chemicals (phytotoxicity) and the concentration thereof observed when these are applied to cucumber.
DE~pTT~n EXPLANATION OF THE lNV~NlION
The coated agricultural chemicals or formulations (hereunder simply referred to as "agricultural chemicals" or "agricultural formulations") of the present invention can be prepared by dissolving 0.1 to 3 parts of at least one member selected from the group consisting of aliphatic acid esters of aliphatic polyols and phospholipids in a proper solvent such as acetone, adding 100 parts of a powdery effective component of an agricultural chemical to the solution, mixing them while stirring and then distilling off the solvent.
-As the aliphatic polyol moieties from which the aliphatic acid esters of aliphatic polyols used herein are produced, there may be employed saturated and unsaturated aliphatic polyols having 3 to 6 carbon atoms and preferred are glycerin, propylene glycol, sorbitol and sorbitan.
On the other hand, examples of the aliphatic acid moieties of the aliphatic aicd esters of polyols herein used are individual aliphatic acids such as saturated aliphatic acids, for instance, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid and behenic acid; or unsaturated aliphatic acids, for instance, oleic acid, linolic acid, linolenic acid and ricinoleic acid; mixed aliphatic acids such as those naturally derived from animals or plants, for instance, tallow, cottonseed oil, rapeseed oil and hardened oil.
Examples of the aliphatic acid esters of the aliphatic polyols as one of main components of the coated agricultural chemicals of the invention are mono-, di- or triesters prepared by esterifying or ester-interchanging the foregoing aliphatic polyols and aliphatic acids, in particular sorbitan monolaurate, sorbitan monostearate, glycerin monooleate, glycerin monooctoate, glycerin mono-soyabean oil fatty acid ester, glycerin mono-cottonseed oil fatty acid ester, triglycerin monooleate, glycerin monopalmitate and polyglycerin fatty acid esters are preferably used.
Moreover, examples of the phospholipids used herein are phytolecithin derived from plant's oils and egg yolk lecithin; and phosphatidylcholine, phosphatidylethanolamine and phosphatidylinositol separated therefrom.
The effective components of the agricultural chemicals of the present invention may be any agricultural chemicals which are in the form of solid powder at ordinary temperature and examples thereof include various - germicides, insecticides and herbicides for agricultural and horticultural use. The effective components may be water-insoluble ones, but preferably water-soluble ones.
Specific examples of the effective components of the agricultural chemicals include ordinary agricultural chemicals such as copper 8-oxyquinoline, basic copper sulfate, basic copper chloride, copper(II) chloride, basic copper carbonate, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, antibiotic-polyoxine complex, o,o-diethyl-s-benzylthiophosphate, 2-sec-butylphenyl-N-methylcarbamate and o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate; and sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, caIcium carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium chloride, potassium chloride, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate which are highly safe against animals and plants.
In the coated agricultural chemicals, the amount of the coating agent, i.e., aliphatic acid esters of aliphatic polyols and/or phospholipids ranges from 0.1 to 3 parts per 100 parts of the effective component. This is because if the amount is outside the foregoing range, the following problems arises when the agricultural chemicals are used by diluting these with water. In other words, if the amount of the coating agent is less than 0.1 part, the agricultural chemicals cannot effectively be emulsified. On the other hand, if it is more than 3 parts, the agricultural chemicals cannot frequently be emulsified effectively since the ester portions are separated and hence the coating film cannot be maintained. However, such an emulsion can be obtained depending on the kinds of the effective component of the agricultural chemicals.
The particle size of the effective components of the agricultural chemicals is preferably adjusted so that it passes through a sieve of 100 mesh, more preferably 200 to 400 mesh, since it is difficult to maintain the coating film if the particle size is too large.
The coated agricultural chemicals of the present invention may further comprise auxiliary agents commonly incorporated in compositions of agricultural chemicals such as surfactants, which do not destroy the emulsion, for instance, spreading agents, wetting and spreading agents and anchorages according to need and then are converted to agricultural formulations.
The concentration thereof to be sprayed varies dependent upon the kinds of the effective components and is not limited to a specific range, but preferred concentration thereof ranges from about 1 to 500 ppm.
The agricultural formulations of the present invention will hereunder be explained in more specifically with reference to Examples, but the invention is not restricted - to these specific Examples. Moreover, the effects practically attained by the present invention will also be discussed below in comparison with Comparative Examples.
Example 1 Glycerin monooleate (2 g) was dissolved in 100 cc of acetone. Then 80 g of fine powder of sodium hydrogen carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powdery product. To the powdery product there was added 10 g of powdery sodium casein and the ingredients were admixed to form a powdery hydrated formulation having good flowability.
Example 2 Polyglycerin fatty acid ester (1 g) was dissolved in 100 cc of acetone. Then 80 g of fine powder of sodium hydrogen carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain a wettable powder. ~ - -Example 3 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of sodium carbonate, 90% of which passed through - a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powdery product. To the powdery product there was added 10 g of powdery sodium casein and these ingredients were admixed to form a wettable powder having good flowability.
Example 4 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of potassium carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powdery product. To the powdery product there was added 10 g of powdery sodium casein and these ingredients were admixed to form a wettable powder having good flowability.
Example 5 Glycerin monooleate ~0.5 g) and glycerin monooctoate - (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of ammonium carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added 10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good flowability.
Example 6 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of ammonium hydrogen carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added -10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good flowability.
Example 7 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of potassium hydrogen carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added 10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good flowability.
Example 8 Glycerin monooleate (2.5 g) and glycerin monooctoate (l.S g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of potassium chloride, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added 10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good flowability.
Example 9 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of sodium chloride, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring tne mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added 10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good f~owability.
Example 10 Glycerin monooctoate (0.8 g) was dissolved in 100 cc of acetone. To the solution 80 g of Benlate (methyl-l-(butylcarbamoyl)-2-benzimidazolecarbamate) was added, followed by sufficiently stirring the mixture, then completely distilling off the solvent to obtain a wettable powder.
Example 11 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.2 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of Polyoxin AL (antibiotic-polyoxin complex) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of white carbon was added to the powder to form a wettable powder having good flowability.
Example 12 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.2 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of Kitazin P (o,o-diethyl-s-- benzylthiophosphate) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of white carbon was added to the powder to form a wettable powder having good flowability.
Example 13 Polyglycerin fatty acid ester (0.5 g) and glycerin monooctoate (0.2 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of Bassa (BPMC: 2-sec-butylphenyl-N-methylcarbamate) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of white carbon was added to the powder to form a wettable powder having good flowability.
Example 14 Polyglycerin fatty acid ester (0.5 g) and glycerin monooctoate (0.2 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of DEP (o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of-white carbon was added to the powder to form a wettable powder having good flowability.
Example 15 Polyglycerin fatty acid ester (0.5 g), glycerin monooctoate (0.2 g) and glycerin monooleate (0.1 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of Bialaphos (see Journal of Antibiotics (J. A.), 1983, Vol. 36, No. 8, pp. 1040 - 1044) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of white carbon was added to the powder to form a wettable powder having good flowability.
-Test Examples 1 to 13 The effects achieved by aqueous solutions of various kinds of coated carbonates and hydrogen carbonates of the present invention were estimated and were compared with those achieved by aqueous solutions of the aforesaid agricultural formulatiGns (J.P. KOKAI No. 63-233902) and conventional agricultural chemicals.
The comparison between these results was performed by preparing solutions of each agricultural chemical having concentrations of 500 and 200 ppm, determining prevention values (%) at 4 and 6 days after the application or spraying and simultaneously estimating phytotoxicity of the agricultural chemicals used. The results observed are listed ' in Table I.
In Table I, the prevention values of the solutions having a concentration of 200 ppm is given in brackets. On the other hand, the phytotoxicity of each agricultural chemical was almost the same regardless of the concentration of the solutions (200 and 500 ppm) and thus the results were summarized and,listed therein.
For the purpose of comparison, the effect observed when a solution free of effective components was used is also listed in Table I as a control.
It is found, from the results summarized in. Table I, that the coated agricultural formulations of the present invention are effective and show extremely high prevention values even when they were used in a low concentration such as 200 and 500 ppm compared with the results observed on the conventional agricultural chemicals and agricultural formulations.
Table I: The prevention effect of various coated carbonates, hydrogen carbonates on mildew of cucumber~
Test No. Formulation Concn. Prevention Value Phyto-tested (ppm)(~) toxici-4 days 6 days ty Test 1 coated NaHCO3 50094(90) 90(85) none (Ex.1) formulation (200) NaHCO3 50051(21) 47(18) none formulation (200) NaHCO3 500 18(0) 10(0) none (200) Test 2 coated Na2CO3 500100(89) 100(84) none (Ex.3) formulation (200) Na2CQ3 50047(17) 42(13) none formulation (200) Na2C3 500 10(1) 5(0) none (200) Table I (continued) Test No. Formulation Concn. Prevention Value Phyto-tested (ppm)(%) toxici-4 days 6 days ty Test 3 coated K2CO3 500100(91) 98(88) none (Ex.4) formulation (200) K2CO3 50048(11) 46(11) none formulation (200) K2CO3 500 16(0) 11(0) none (200) Test 4 coated CaCO3 500100(87) 100(81) none formulation (200) CaCO3 50041(10) 32(7) none formulation (200) CaCO3 500180(0) 10(0) none (200) - Test 5 coated (NH4)2CO3 500100(86) 100(82) none (Ex.5) formulation (200) (NH4)2Co3 500 38(5) 29(0) none formulation (200) (NH4)2Co3 500 7(0) 3(0) none (200) Test 6 coated (NH4)HCO3 50097(83) 95(80) none (Ex.6) formulation (200) (NH4)HCO3 500 35(8) 30(0) none formulation (200) (NH4)HCO3 500 8(0) 5(0) none (200) Table I (continued) Test No. Formulation Concn. Prevention Value Phyto-teæted (ppm)(%) toxici-4 days 6 days ty Test 7 coated NaCl 50097(90) 92(85) none (Ex.9) formulation (200) NaCl 50050(21) 44(21) none formulation (200) NaCl 500 20(0) 15(0) none (200) Test 8 coated KCl 500100(94; 98(91) none - (Ex.8) formulation (200) XCl 500 47(0) 45(0) none formulation (200) XCl 500 20(0) 10(0) none (200) Test 9 coated XHC03 500 100(98) 100(92) none (Ex.7) formulation (200) XHC03 50042(15) 38(13) none formulation (200) XHCO3 500 20(0) 20(0) none (200) Test 10 coated Na2HPO4 50098(90) 91(81) none formulation (200) Na2HPO4 50032(22) 30(22) none formulation (200) Na2HPO4 50020(10) 20(5) none (200) Table I (continued) Test No. Formulation Concn. Prevention Value Phyto-tested (ppm)(~) toxici-4 days 6 days ty Test 11 coated NaH2PO4 500100(100) 100(93) none formulation (200) NaH2PO4 50040(23) 30(25) none formulation (200) NaH2PO4 500 30(5) 28(0) none (200) Test 12 coated K2HPO4 50098(94) 93(93) none formulation (200) K2HPO4 50028(14) 25(12) none formulation (200) K2HPO4 500 25(5) 20(0) none (200) - Test 13 coated KH2PO4 500100(90) 97(89) none formulation (200) KH2PO4 50038(11) 32(11) none formulation (200) KH2PO4 500 31(3) 15(1) none (200) Control none 0(0) 0(0) 0(0) none Note: The prevention values given in the brackets correspond to the data obtained when the formulation was used at the concentration given in the brackets.
Test Examples 14 to 19 The coated agricultural formulations of the present invention were prepared by using methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate, antibiotic-polyoxin complex, o,o-diethyl-s-benzylthiophosphate, 2-sec-butylphenyl-N-methylcarbamate, o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate and Bialaphos. In order to examine the uariation in effect with the change in the concentration, the prevention value for grey mildew of cucumber and tomato, the rate of death for thrips plami and tabacco cutdown (Prodenia litura), and efficiency index for culy dock (Rumex obtusifolius L.) were estimated. The prevention value was estimated from the following relation:
Number of Rotten Parts in T.D.
Prevention = (1 - ) X 100 - Value (%) Number of Rotten Parts in N.T.D.
In addition, the efficiency index was calculated from the following relation:
Survival Rate of Insects in T.D.
Efficiency = (1 - ) X 100 Index Survival Rate of Insects in N.T.D.
In these relations, T.D. and N.T.D. represent treated domain and non-treated domain respectively.
-The results observed are summarized in Table II below.
For grey mildew of cucumber and tomato, the prevention value of the coated methyl 1- ( butylcarbamoyl ) -2-benzimidazolecarbamate was remarkably enhanced in the concentration range of 10 to 80 ppm as the concentration increases, compared with the aqueous solution of the same agricultural chemical co,l~,elltionally used.
The prevention values of the coated antibiotic-- polyoxin complex for grey mildew of cucumber and tomato were all not less than 90% between 25 and 100 ppm while those of the aqueous solution of the conventional agricultural formulations were all not more than 50%.
In addition, it is found that the coated o,o-diethyl-s-benzylthiophosphate exhibits the prevention values for grey mildew of tomato ranging from 89 to 98% between 60 and 480 ppm while those of the aqueous solution of the non-coated one ranges from 24 to 76%. This clearly indicates that the coated formulation is effective to such a disease.
The coated 2-sec-butylphenyl-N-methylcarbamate exhibits the rate of death for thrips palmi ranging from 75 to 96%
between 50 and 150 ppm while that of the ordinary aqueous solution of the non-coated one ranges from 5 to 18%.
The coated o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate exhibits the rate of death for tabacco cutdown ranging from 76 to 100% between 50 and 150 ppm while that of the ordinary aqueous solution of the non-coated one ranges from 0 to 15%. It is also found that the coated so-called Bialaphos increases the efficiency index for culy dock 2 to 3 times larger than that of an aqueous . solution of the non-coated one in a concentration range of 60 to 500 ppm.
Table II: Plevention Effect of Various Coated Formulations on Various diseases Test Formulation Tested Concn. P.V. for P.V. for No. (ppm) G.M. of G.M. of cucumber tomato Ex. 10 (coated 10 91 87 Benlate) ditto 20 92 92 ditto 40 95 97 ditto 80 96 99 Benlate 10 21 20 ditto 20 33 37 ditto - 40 57 51 ditto 80 71 70 -Ex. 11 (coated poly-25 90 92 oxin AL) ditto 50 95 96 ditto 100 98 99 polyoxin AL 25 0 0 ditto 50 11 8 ditto 100 42 25 16 Ex. 12 (coated 60 89 Ritazin-P) ditto 120 93 ditto 240 96 ditto 480 98 Ritazin-P 60 24 ditto 120 33 ditto 240 50 ditto 480 76 Table II (continued) Test Formulation Concn. Rate of Rate of Efficiency No. Tested (ppm) death(%) Death(%) Index for thrips for tabacco for culy palmi cutdown dock 17 Ex. 13 (coated 50 75 Bassa) ditto 100 89 ditto 150 96 Bassa (BPMC) 50 5 ditto 100 10 ditto 150 18 18 Ex. 14 (coated50 76 DEP) ditto 100 92 ditto 150 100 ditto 200 100 ditto 100 0 ditto 150 15 19 Ex. 15 (coated-~60 - 4.1 Bialaphos) ditto 125 4.9 ditto 250 5.7 ditto 500 7.2 Bialaphos 60 0.4 ditto 125 0.9 ditto 250 1.7 ditto 500 2.4 *: P.V. and G.M. mean prevention value and grey mildew, respectively.
Test Examples 20 to 32 Aqueous solutions of each of the coated agricultural formulations, agricultural formulations or agricultural chemicals having concentrations of 200 and 500 ppm were prepared and the prevention values and the phytotoxicity thereof were determined. The results are summarized in Table III.
-In each Test Nos. 20 to 32, the coated formulations of the present invention exhibit prevention values higher than those of the foregoing agricultural formulations and simple aqueous solution of agricultural chemicals. In all the tests, the phytotoxicity of these agricultural chemicals was not observed.
Table III: -The; prevention effect of various coated carbonates, hydrogen carbonates on citrus melanose.
Test No. Formulation Concn. Prevention Phytoto-tested (ppm) Value (%) xicity -coated NaHCO3 500100(100) none formulation (200) NaHCO3 500 70(21) none formulation (200) NaHCO3 500 40(3) none (200) Table III (continued) Test No. Formulation Concn. Prevention Phytoto-tested (ppm) Value (%) xicity 21 coated Na2CO3 500 98(95) none formulation (200) Na2C3 500 65(18) none formulation (200) Na2C3 500 38(0) none (200) 22 coated K2CO3 500 100(93) none formulation ( 200) K2CO3 500 67(21) none formulation ( 200) K2CO3 500 35(11) none (200) 23 coated CaCO3 500 92(90) none formulation ( 200) CaCO3 500 62(12) none -i formulation ~200j -CaCO3 500 30(5) ncne (200) 24 cGated (NH4)2CO3 50C 88~80) none formulation (200) (NH4)2Co3 500 57(10) none formulation ( 200) (NH4)2Co3 500 19(0) none (200) Table III (continued) Test No. Formulation Concn. Prevention Phytoto-tested (ppm) Value (%) xicity coated (NH4)HCO3 500 86(80) none formulation (200) (NH4)HCO3 500 53(7) none formulation (200) (NH4)HCO3 500 16(0) none (200) 26 coated NaCl 500 92(90) none formulation (200) NaCl 500 84(22) none formulation (200) NaCl 500 22(2) none (200) 27 coated RCl 500 94(90) none formulation (200) RCl 500 62(12) none formulation (200) KCl 500 31(0) none (200) 28 coated RHCO3 500 94(90~ ~ne formulation (200) KHCO3 500 57(23) none formulation (200) RHCO3 500 51(3) none (200) Table III (continued) Test No. Formulation Concn. Prevention nytoto-tested (ppm) Value (%) ~:icity 29 coated Na2HPO4 500 87(80) none formulation (200) Na2HPO4 500 41(11) none formulation (200) Na2HPO4 500 20(0) none (200) coated NaH2PO4 500 86(83) none formulation (200) NaH2PO4 500 22(12) none formulation (200) NaH2PO4 500 10(0) none (200) 31 coated K2HPO4 500 88(85) none formulation (200) K2HPO4 - 500 31(15) none formulation (200) K2HPO4 500 12(5) none (200) 32 coated KH2PO4 500 87(81) none formulation (200) KH2PO4 500 34(14) none formulation (200) KH2PO4 500 7(3) none (200) Control none 0(0) 0(0) none Note: The prevention values given in the brackets corresponds to the data obtained when the agricultural chemicals were used at the concentration given in the brackets.
The prevention effect of the agricultural formulations on black spot disease of oranges were exArined with respect to the aqueous solution of NaHC03 (~ ), a formulation of J.P. KOKAI No. 63-233902 (this could be prepared by suspending 80 to 200 parts of NaHCO3 in 100 parts of 3/1 mixture of oleic acid monoglyceride and glycerin monooctoate;D ---~) and the coated NaHCO3 formulation (O --- O ) while changing the concentration thereof and the results were plotted in Fig. 1 (Test Example 20).
When the concentration was changed between 0 and 2,000 ppm, the prevention value of the aqueous solution of conventional agricultural chemicals reaches only 10% at 2,000 ppm and the formulation of J.P. KOKAI No. 63-233902 requires about 1,000 ppm to attain the prevention value of - 80%. On the contrary, tha prevention value of as high as 97%
was attained by using the coated formulation of the invention only at 250 ppm. This clearly indicates that the coated formulation of the invention is extremely effective even at a concentration lower than that of the other two formulations.
Fig. 2 is a diagram illustrating the relationship between the prevention value and three different forms of the formulation used while taking into consideration the state of occurrence of citrus melanose (number of spots due to disease: 2,000/leaf ( O ); 900/leaf (~) and 400/leaf (Q
)) and changing the concentration (250, 500 and 2,000 ppm).
In this figure, A denotes the coated formulation of the invention, B NaHCO3 formulation and C an aqueous solution of uncoated NaHCO3. . PA
As shown in Fig. 2, the coated formulation of the invention shows high prevention values at every concentrations examined regardless of whether the state of disease is severe and effectively suppresses the citrus melanose. On the other hand, the agricultural formulation of J.P. KOKAI No. 63-233902 (this was prepared by suspending 80 to 200 parts of NaHCO3 in 100 parts of 3/1 mixture of oleic acid monoglyceride and glycerin monooctoate) and an - aqueous solution of the uncoated NaHCO3 are effective only at a relatively low number of spots due to disease even when -they are used in a high c~ncentration. In other word, they can be effective only at the initial state of the disease.
Fig.3 shows the prevention values of each agricultural formulations at each concentration with respect to mildew of cucumber when the state of the disease is medium (200/leaf).
In this figure, O --- O, ~--- D and ~ --- ~ represent the coated NaHCO3 formulation, NaHCO3 formulation and aqueous solution of NaHCO3 respectively (Test Example 1).
As seen from the results shown in Fig. 3, the coated agricultural formulation of the present invention shows effects superior to those observed on the other agricultural chemicals.
Fig. 4 is a diagram illustrating the relationship between the prevention value and three different forms of the NaHCO3 formulation used while taking the state of generation of mildew of cucumber into consideration and changing the concentration as in Fig. 2.
The coated formulation of the invention can effectively sup~less the mildew of cucumber in severe state at each concentration e~Amined (250, 500 and 1,000 ppm) and ~ is found to be a preferred agricultural chemical. In this fig~-re, ~ , ~ , o / and ~ represent data corresponding to the number of spots due to disease of 40, 105, 200, 280, 510 ~and 975/leaf respectively. In addition, A, B and C are the same as those defined in Fig. 2.
Fig. 5 is a diagram illustrating the relationship between the prevention value of NaHCO3 formulations and the forms thereof used with respect to mildew of cucumber in severe state (the number of spots due to the disease:
450/leaf) while changing the concentration of the formulations. It is found that the coated formulation of the invention can effectively suppress the mildew of cucumber in severe state compared with aqueous solution and agricultural formulation of J.P. KOKAI No. 63-233902.
Fig. 6 shows the relation between the concentration of each agricultural formulation and the number of spots (phytotoxicity).
~ 334823 It is noted that unlike the conventional aqueous solution, the agricultural formulation of J.P. KOKAI No. 63-233902 and the coated formulation of the invention do not show phytotoxicity at a concentration of not more than 4,000 ppm.
AS dicussed above in detail, the coated agricultural formulation of the present invention exhibits the prevention - - value superio~ t~ thio~e of the uncoated a,gricult.u;r~
chemicals and the aforesaid agricultural formulations (J.P.
KOKAI No. 63-233902).
.If using an aqueous solution of conventional agricultural chemicals and the foregoing agricultural formulation, the number of spots due to disease in general increases and the prevention value thereof is lowered as the disease proceeds while the coated agricultural formulation of the invention does not show such tendency and shows stable efficiency.
The phytotoxicity of the coated formulation of the invention, which is estimated on the basis of the number of spots due to disease, is almost the same as that observed on the control (free from agricultural chemicals).
TITLE OF THE lNV~:N ~ lON
Coated Agricultural Chemicals RACRG~OUND OF THE lNv~NTlON
Field of the Invention - The present invent~on relates to coated agricultural -chemicals or formulations which can exhibit s~fficiently-high efficiency even at a concentration lower than that of conventionally used.
Description of the Prior Art Hitherto, there have widely been used such heavy metal compounds as cupreous agents, mercurials and arsenicals;
organochlorine agricultural chemicals and organophosphorus agricultural chemicals as formulations of agricultural chemicals. However, all of these agricultural chemicals are not only harmful to human body and animals but also contaminate the soil which leads to enviloru..ental pollution developed into a severe social problem accompanied by the use of effective amount thereof.
Under such circumstances, Japanese Patent Publication for Opposition Purpose (hereunder referred to as "J.P.
ROKOKU") No. 57-48525 teaches that a fungicide mainly .~
composed of an ester of an aliphatic polyol and an aliphatic acid and sodium hydrogen carbonate shows a prevention effect on various blight of plants and those observed during storing fruits and is highly safe with respect to human body, ~ni~=ls and plants.
However, the agricultural chemicals prepared according to such a method must be used in a high concentration in order to achieve a desired efficiency when they are used in an amount comparable to that-of the conventional ones and on the contrary, if the concentration thereof is limited to a low level, a desired efficiency is attained only when they are used in a large amount.
To eliminate such disadvantages, the inventors of this invention developed a formulation of agricultural chemicals (see Japanese Patent Unexamined Published Application (hereunder referred to as "J.P. KOKAI") No. 63-233902).
However, such a formulation is not still satisfied since it provides a desired effect only when the concentration of the effective component is relatively high, and when the state of blight occurrence is severe, its effect becomes low.
SUMMARY OF THE lNv~NllON
Accordingly, an object of the present invention is to provide coated agricultural chemicals or formulations which exhibit high efficiency even at a low concentration.
The aforementioned object of the present invention can be achieved by providing a coated agricultural chemical which comprises a powdery effective component of an agricultural chemical coated with at least one member selected from the group consisting of aliphatic acid esters of aliphatic polyols and phospholipids in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the effective component.
BRIEF EXPLANATION OF THE DRAWINGS
The present invention will hereunder be explained in more detail with reference to the accompanied drawings, wherein:
Fig. 1 shows the prevention value of various agricultural formulations for black spot disease of oranges, plotted against the concentration of the formulation;
Fig. 2 shows the relation between the prevention value of various agricultural formulations and the forms thereof while taking the number of spots due to disease into consideration and changing the concentration of the formulations;
Fig. 3 shows the relation between the prevention value of various formulations with respect to mildew of cucumber and the concentration thereof, observed when the state of disease is medium (the number of spots due to disease: 200/leaf);
-Fig. 4 shows the relation between the prevention value of various agricultural formulations for mildew of cucumber and the forms thereof while taking the state of the disease into consideration;
Fig. 5 shows the relation between the prevention value of various agricultural formulations and the concentration thereof observed when the state of disease is severe; and Fig. 6 is attached hereto to demonstrate the degree of - phytotoxicity of the coated NaHCO3 formulation, NaHCO3 formulation and an aqueous solution of non-coated NaHCO3 and shows the relation between the number of spots due to agricultural chemicals (phytotoxicity) and the concentration thereof observed when these are applied to cucumber.
DE~pTT~n EXPLANATION OF THE lNV~NlION
The coated agricultural chemicals or formulations (hereunder simply referred to as "agricultural chemicals" or "agricultural formulations") of the present invention can be prepared by dissolving 0.1 to 3 parts of at least one member selected from the group consisting of aliphatic acid esters of aliphatic polyols and phospholipids in a proper solvent such as acetone, adding 100 parts of a powdery effective component of an agricultural chemical to the solution, mixing them while stirring and then distilling off the solvent.
-As the aliphatic polyol moieties from which the aliphatic acid esters of aliphatic polyols used herein are produced, there may be employed saturated and unsaturated aliphatic polyols having 3 to 6 carbon atoms and preferred are glycerin, propylene glycol, sorbitol and sorbitan.
On the other hand, examples of the aliphatic acid moieties of the aliphatic aicd esters of polyols herein used are individual aliphatic acids such as saturated aliphatic acids, for instance, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid and behenic acid; or unsaturated aliphatic acids, for instance, oleic acid, linolic acid, linolenic acid and ricinoleic acid; mixed aliphatic acids such as those naturally derived from animals or plants, for instance, tallow, cottonseed oil, rapeseed oil and hardened oil.
Examples of the aliphatic acid esters of the aliphatic polyols as one of main components of the coated agricultural chemicals of the invention are mono-, di- or triesters prepared by esterifying or ester-interchanging the foregoing aliphatic polyols and aliphatic acids, in particular sorbitan monolaurate, sorbitan monostearate, glycerin monooleate, glycerin monooctoate, glycerin mono-soyabean oil fatty acid ester, glycerin mono-cottonseed oil fatty acid ester, triglycerin monooleate, glycerin monopalmitate and polyglycerin fatty acid esters are preferably used.
Moreover, examples of the phospholipids used herein are phytolecithin derived from plant's oils and egg yolk lecithin; and phosphatidylcholine, phosphatidylethanolamine and phosphatidylinositol separated therefrom.
The effective components of the agricultural chemicals of the present invention may be any agricultural chemicals which are in the form of solid powder at ordinary temperature and examples thereof include various - germicides, insecticides and herbicides for agricultural and horticultural use. The effective components may be water-insoluble ones, but preferably water-soluble ones.
Specific examples of the effective components of the agricultural chemicals include ordinary agricultural chemicals such as copper 8-oxyquinoline, basic copper sulfate, basic copper chloride, copper(II) chloride, basic copper carbonate, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, antibiotic-polyoxine complex, o,o-diethyl-s-benzylthiophosphate, 2-sec-butylphenyl-N-methylcarbamate and o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate; and sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, caIcium carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium chloride, potassium chloride, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate which are highly safe against animals and plants.
In the coated agricultural chemicals, the amount of the coating agent, i.e., aliphatic acid esters of aliphatic polyols and/or phospholipids ranges from 0.1 to 3 parts per 100 parts of the effective component. This is because if the amount is outside the foregoing range, the following problems arises when the agricultural chemicals are used by diluting these with water. In other words, if the amount of the coating agent is less than 0.1 part, the agricultural chemicals cannot effectively be emulsified. On the other hand, if it is more than 3 parts, the agricultural chemicals cannot frequently be emulsified effectively since the ester portions are separated and hence the coating film cannot be maintained. However, such an emulsion can be obtained depending on the kinds of the effective component of the agricultural chemicals.
The particle size of the effective components of the agricultural chemicals is preferably adjusted so that it passes through a sieve of 100 mesh, more preferably 200 to 400 mesh, since it is difficult to maintain the coating film if the particle size is too large.
The coated agricultural chemicals of the present invention may further comprise auxiliary agents commonly incorporated in compositions of agricultural chemicals such as surfactants, which do not destroy the emulsion, for instance, spreading agents, wetting and spreading agents and anchorages according to need and then are converted to agricultural formulations.
The concentration thereof to be sprayed varies dependent upon the kinds of the effective components and is not limited to a specific range, but preferred concentration thereof ranges from about 1 to 500 ppm.
The agricultural formulations of the present invention will hereunder be explained in more specifically with reference to Examples, but the invention is not restricted - to these specific Examples. Moreover, the effects practically attained by the present invention will also be discussed below in comparison with Comparative Examples.
Example 1 Glycerin monooleate (2 g) was dissolved in 100 cc of acetone. Then 80 g of fine powder of sodium hydrogen carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powdery product. To the powdery product there was added 10 g of powdery sodium casein and the ingredients were admixed to form a powdery hydrated formulation having good flowability.
Example 2 Polyglycerin fatty acid ester (1 g) was dissolved in 100 cc of acetone. Then 80 g of fine powder of sodium hydrogen carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain a wettable powder. ~ - -Example 3 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of sodium carbonate, 90% of which passed through - a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powdery product. To the powdery product there was added 10 g of powdery sodium casein and these ingredients were admixed to form a wettable powder having good flowability.
Example 4 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of potassium carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powdery product. To the powdery product there was added 10 g of powdery sodium casein and these ingredients were admixed to form a wettable powder having good flowability.
Example 5 Glycerin monooleate ~0.5 g) and glycerin monooctoate - (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of ammonium carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added 10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good flowability.
Example 6 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of ammonium hydrogen carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added -10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good flowability.
Example 7 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of potassium hydrogen carbonate, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added 10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good flowability.
Example 8 Glycerin monooleate (2.5 g) and glycerin monooctoate (l.S g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of potassium chloride, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring the mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added 10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good flowability.
Example 9 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.3 g) were dissolved in 100 cc of acetone. Then 80 g of fine powder of sodium chloride, 90% of which passed through a sieve of 100 mesh, was added to the solution, followed by sufficiently stirring tne mixture and completely distilling off the solvent utilizing a rotary evaporator to obtain powder. To the powder there was added 10 g of powdery sodium casein and the mixture was admixed to form a wettable powder having good f~owability.
Example 10 Glycerin monooctoate (0.8 g) was dissolved in 100 cc of acetone. To the solution 80 g of Benlate (methyl-l-(butylcarbamoyl)-2-benzimidazolecarbamate) was added, followed by sufficiently stirring the mixture, then completely distilling off the solvent to obtain a wettable powder.
Example 11 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.2 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of Polyoxin AL (antibiotic-polyoxin complex) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of white carbon was added to the powder to form a wettable powder having good flowability.
Example 12 Glycerin monooleate (0.5 g) and glycerin monooctoate (0.2 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of Kitazin P (o,o-diethyl-s-- benzylthiophosphate) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of white carbon was added to the powder to form a wettable powder having good flowability.
Example 13 Polyglycerin fatty acid ester (0.5 g) and glycerin monooctoate (0.2 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of Bassa (BPMC: 2-sec-butylphenyl-N-methylcarbamate) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of white carbon was added to the powder to form a wettable powder having good flowability.
Example 14 Polyglycerin fatty acid ester (0.5 g) and glycerin monooctoate (0.2 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of DEP (o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of-white carbon was added to the powder to form a wettable powder having good flowability.
Example 15 Polyglycerin fatty acid ester (0.5 g), glycerin monooctoate (0.2 g) and glycerin monooleate (0.1 g) were dissolved in 100 cc of acetone. To the solution there were added 80 g of Bialaphos (see Journal of Antibiotics (J. A.), 1983, Vol. 36, No. 8, pp. 1040 - 1044) and lactose, followed by sufficiently stirring the mixture and distilling off the solvent therefrom to obtain powdery product. Then 5 g of white carbon was added to the powder to form a wettable powder having good flowability.
-Test Examples 1 to 13 The effects achieved by aqueous solutions of various kinds of coated carbonates and hydrogen carbonates of the present invention were estimated and were compared with those achieved by aqueous solutions of the aforesaid agricultural formulatiGns (J.P. KOKAI No. 63-233902) and conventional agricultural chemicals.
The comparison between these results was performed by preparing solutions of each agricultural chemical having concentrations of 500 and 200 ppm, determining prevention values (%) at 4 and 6 days after the application or spraying and simultaneously estimating phytotoxicity of the agricultural chemicals used. The results observed are listed ' in Table I.
In Table I, the prevention values of the solutions having a concentration of 200 ppm is given in brackets. On the other hand, the phytotoxicity of each agricultural chemical was almost the same regardless of the concentration of the solutions (200 and 500 ppm) and thus the results were summarized and,listed therein.
For the purpose of comparison, the effect observed when a solution free of effective components was used is also listed in Table I as a control.
It is found, from the results summarized in. Table I, that the coated agricultural formulations of the present invention are effective and show extremely high prevention values even when they were used in a low concentration such as 200 and 500 ppm compared with the results observed on the conventional agricultural chemicals and agricultural formulations.
Table I: The prevention effect of various coated carbonates, hydrogen carbonates on mildew of cucumber~
Test No. Formulation Concn. Prevention Value Phyto-tested (ppm)(~) toxici-4 days 6 days ty Test 1 coated NaHCO3 50094(90) 90(85) none (Ex.1) formulation (200) NaHCO3 50051(21) 47(18) none formulation (200) NaHCO3 500 18(0) 10(0) none (200) Test 2 coated Na2CO3 500100(89) 100(84) none (Ex.3) formulation (200) Na2CQ3 50047(17) 42(13) none formulation (200) Na2C3 500 10(1) 5(0) none (200) Table I (continued) Test No. Formulation Concn. Prevention Value Phyto-tested (ppm)(%) toxici-4 days 6 days ty Test 3 coated K2CO3 500100(91) 98(88) none (Ex.4) formulation (200) K2CO3 50048(11) 46(11) none formulation (200) K2CO3 500 16(0) 11(0) none (200) Test 4 coated CaCO3 500100(87) 100(81) none formulation (200) CaCO3 50041(10) 32(7) none formulation (200) CaCO3 500180(0) 10(0) none (200) - Test 5 coated (NH4)2CO3 500100(86) 100(82) none (Ex.5) formulation (200) (NH4)2Co3 500 38(5) 29(0) none formulation (200) (NH4)2Co3 500 7(0) 3(0) none (200) Test 6 coated (NH4)HCO3 50097(83) 95(80) none (Ex.6) formulation (200) (NH4)HCO3 500 35(8) 30(0) none formulation (200) (NH4)HCO3 500 8(0) 5(0) none (200) Table I (continued) Test No. Formulation Concn. Prevention Value Phyto-teæted (ppm)(%) toxici-4 days 6 days ty Test 7 coated NaCl 50097(90) 92(85) none (Ex.9) formulation (200) NaCl 50050(21) 44(21) none formulation (200) NaCl 500 20(0) 15(0) none (200) Test 8 coated KCl 500100(94; 98(91) none - (Ex.8) formulation (200) XCl 500 47(0) 45(0) none formulation (200) XCl 500 20(0) 10(0) none (200) Test 9 coated XHC03 500 100(98) 100(92) none (Ex.7) formulation (200) XHC03 50042(15) 38(13) none formulation (200) XHCO3 500 20(0) 20(0) none (200) Test 10 coated Na2HPO4 50098(90) 91(81) none formulation (200) Na2HPO4 50032(22) 30(22) none formulation (200) Na2HPO4 50020(10) 20(5) none (200) Table I (continued) Test No. Formulation Concn. Prevention Value Phyto-tested (ppm)(~) toxici-4 days 6 days ty Test 11 coated NaH2PO4 500100(100) 100(93) none formulation (200) NaH2PO4 50040(23) 30(25) none formulation (200) NaH2PO4 500 30(5) 28(0) none (200) Test 12 coated K2HPO4 50098(94) 93(93) none formulation (200) K2HPO4 50028(14) 25(12) none formulation (200) K2HPO4 500 25(5) 20(0) none (200) - Test 13 coated KH2PO4 500100(90) 97(89) none formulation (200) KH2PO4 50038(11) 32(11) none formulation (200) KH2PO4 500 31(3) 15(1) none (200) Control none 0(0) 0(0) 0(0) none Note: The prevention values given in the brackets correspond to the data obtained when the formulation was used at the concentration given in the brackets.
Test Examples 14 to 19 The coated agricultural formulations of the present invention were prepared by using methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate, antibiotic-polyoxin complex, o,o-diethyl-s-benzylthiophosphate, 2-sec-butylphenyl-N-methylcarbamate, o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate and Bialaphos. In order to examine the uariation in effect with the change in the concentration, the prevention value for grey mildew of cucumber and tomato, the rate of death for thrips plami and tabacco cutdown (Prodenia litura), and efficiency index for culy dock (Rumex obtusifolius L.) were estimated. The prevention value was estimated from the following relation:
Number of Rotten Parts in T.D.
Prevention = (1 - ) X 100 - Value (%) Number of Rotten Parts in N.T.D.
In addition, the efficiency index was calculated from the following relation:
Survival Rate of Insects in T.D.
Efficiency = (1 - ) X 100 Index Survival Rate of Insects in N.T.D.
In these relations, T.D. and N.T.D. represent treated domain and non-treated domain respectively.
-The results observed are summarized in Table II below.
For grey mildew of cucumber and tomato, the prevention value of the coated methyl 1- ( butylcarbamoyl ) -2-benzimidazolecarbamate was remarkably enhanced in the concentration range of 10 to 80 ppm as the concentration increases, compared with the aqueous solution of the same agricultural chemical co,l~,elltionally used.
The prevention values of the coated antibiotic-- polyoxin complex for grey mildew of cucumber and tomato were all not less than 90% between 25 and 100 ppm while those of the aqueous solution of the conventional agricultural formulations were all not more than 50%.
In addition, it is found that the coated o,o-diethyl-s-benzylthiophosphate exhibits the prevention values for grey mildew of tomato ranging from 89 to 98% between 60 and 480 ppm while those of the aqueous solution of the non-coated one ranges from 24 to 76%. This clearly indicates that the coated formulation is effective to such a disease.
The coated 2-sec-butylphenyl-N-methylcarbamate exhibits the rate of death for thrips palmi ranging from 75 to 96%
between 50 and 150 ppm while that of the ordinary aqueous solution of the non-coated one ranges from 5 to 18%.
The coated o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate exhibits the rate of death for tabacco cutdown ranging from 76 to 100% between 50 and 150 ppm while that of the ordinary aqueous solution of the non-coated one ranges from 0 to 15%. It is also found that the coated so-called Bialaphos increases the efficiency index for culy dock 2 to 3 times larger than that of an aqueous . solution of the non-coated one in a concentration range of 60 to 500 ppm.
Table II: Plevention Effect of Various Coated Formulations on Various diseases Test Formulation Tested Concn. P.V. for P.V. for No. (ppm) G.M. of G.M. of cucumber tomato Ex. 10 (coated 10 91 87 Benlate) ditto 20 92 92 ditto 40 95 97 ditto 80 96 99 Benlate 10 21 20 ditto 20 33 37 ditto - 40 57 51 ditto 80 71 70 -Ex. 11 (coated poly-25 90 92 oxin AL) ditto 50 95 96 ditto 100 98 99 polyoxin AL 25 0 0 ditto 50 11 8 ditto 100 42 25 16 Ex. 12 (coated 60 89 Ritazin-P) ditto 120 93 ditto 240 96 ditto 480 98 Ritazin-P 60 24 ditto 120 33 ditto 240 50 ditto 480 76 Table II (continued) Test Formulation Concn. Rate of Rate of Efficiency No. Tested (ppm) death(%) Death(%) Index for thrips for tabacco for culy palmi cutdown dock 17 Ex. 13 (coated 50 75 Bassa) ditto 100 89 ditto 150 96 Bassa (BPMC) 50 5 ditto 100 10 ditto 150 18 18 Ex. 14 (coated50 76 DEP) ditto 100 92 ditto 150 100 ditto 200 100 ditto 100 0 ditto 150 15 19 Ex. 15 (coated-~60 - 4.1 Bialaphos) ditto 125 4.9 ditto 250 5.7 ditto 500 7.2 Bialaphos 60 0.4 ditto 125 0.9 ditto 250 1.7 ditto 500 2.4 *: P.V. and G.M. mean prevention value and grey mildew, respectively.
Test Examples 20 to 32 Aqueous solutions of each of the coated agricultural formulations, agricultural formulations or agricultural chemicals having concentrations of 200 and 500 ppm were prepared and the prevention values and the phytotoxicity thereof were determined. The results are summarized in Table III.
-In each Test Nos. 20 to 32, the coated formulations of the present invention exhibit prevention values higher than those of the foregoing agricultural formulations and simple aqueous solution of agricultural chemicals. In all the tests, the phytotoxicity of these agricultural chemicals was not observed.
Table III: -The; prevention effect of various coated carbonates, hydrogen carbonates on citrus melanose.
Test No. Formulation Concn. Prevention Phytoto-tested (ppm) Value (%) xicity -coated NaHCO3 500100(100) none formulation (200) NaHCO3 500 70(21) none formulation (200) NaHCO3 500 40(3) none (200) Table III (continued) Test No. Formulation Concn. Prevention Phytoto-tested (ppm) Value (%) xicity 21 coated Na2CO3 500 98(95) none formulation (200) Na2C3 500 65(18) none formulation (200) Na2C3 500 38(0) none (200) 22 coated K2CO3 500 100(93) none formulation ( 200) K2CO3 500 67(21) none formulation ( 200) K2CO3 500 35(11) none (200) 23 coated CaCO3 500 92(90) none formulation ( 200) CaCO3 500 62(12) none -i formulation ~200j -CaCO3 500 30(5) ncne (200) 24 cGated (NH4)2CO3 50C 88~80) none formulation (200) (NH4)2Co3 500 57(10) none formulation ( 200) (NH4)2Co3 500 19(0) none (200) Table III (continued) Test No. Formulation Concn. Prevention Phytoto-tested (ppm) Value (%) xicity coated (NH4)HCO3 500 86(80) none formulation (200) (NH4)HCO3 500 53(7) none formulation (200) (NH4)HCO3 500 16(0) none (200) 26 coated NaCl 500 92(90) none formulation (200) NaCl 500 84(22) none formulation (200) NaCl 500 22(2) none (200) 27 coated RCl 500 94(90) none formulation (200) RCl 500 62(12) none formulation (200) KCl 500 31(0) none (200) 28 coated RHCO3 500 94(90~ ~ne formulation (200) KHCO3 500 57(23) none formulation (200) RHCO3 500 51(3) none (200) Table III (continued) Test No. Formulation Concn. Prevention nytoto-tested (ppm) Value (%) ~:icity 29 coated Na2HPO4 500 87(80) none formulation (200) Na2HPO4 500 41(11) none formulation (200) Na2HPO4 500 20(0) none (200) coated NaH2PO4 500 86(83) none formulation (200) NaH2PO4 500 22(12) none formulation (200) NaH2PO4 500 10(0) none (200) 31 coated K2HPO4 500 88(85) none formulation (200) K2HPO4 - 500 31(15) none formulation (200) K2HPO4 500 12(5) none (200) 32 coated KH2PO4 500 87(81) none formulation (200) KH2PO4 500 34(14) none formulation (200) KH2PO4 500 7(3) none (200) Control none 0(0) 0(0) none Note: The prevention values given in the brackets corresponds to the data obtained when the agricultural chemicals were used at the concentration given in the brackets.
The prevention effect of the agricultural formulations on black spot disease of oranges were exArined with respect to the aqueous solution of NaHC03 (~ ), a formulation of J.P. KOKAI No. 63-233902 (this could be prepared by suspending 80 to 200 parts of NaHCO3 in 100 parts of 3/1 mixture of oleic acid monoglyceride and glycerin monooctoate;D ---~) and the coated NaHCO3 formulation (O --- O ) while changing the concentration thereof and the results were plotted in Fig. 1 (Test Example 20).
When the concentration was changed between 0 and 2,000 ppm, the prevention value of the aqueous solution of conventional agricultural chemicals reaches only 10% at 2,000 ppm and the formulation of J.P. KOKAI No. 63-233902 requires about 1,000 ppm to attain the prevention value of - 80%. On the contrary, tha prevention value of as high as 97%
was attained by using the coated formulation of the invention only at 250 ppm. This clearly indicates that the coated formulation of the invention is extremely effective even at a concentration lower than that of the other two formulations.
Fig. 2 is a diagram illustrating the relationship between the prevention value and three different forms of the formulation used while taking into consideration the state of occurrence of citrus melanose (number of spots due to disease: 2,000/leaf ( O ); 900/leaf (~) and 400/leaf (Q
)) and changing the concentration (250, 500 and 2,000 ppm).
In this figure, A denotes the coated formulation of the invention, B NaHCO3 formulation and C an aqueous solution of uncoated NaHCO3. . PA
As shown in Fig. 2, the coated formulation of the invention shows high prevention values at every concentrations examined regardless of whether the state of disease is severe and effectively suppresses the citrus melanose. On the other hand, the agricultural formulation of J.P. KOKAI No. 63-233902 (this was prepared by suspending 80 to 200 parts of NaHCO3 in 100 parts of 3/1 mixture of oleic acid monoglyceride and glycerin monooctoate) and an - aqueous solution of the uncoated NaHCO3 are effective only at a relatively low number of spots due to disease even when -they are used in a high c~ncentration. In other word, they can be effective only at the initial state of the disease.
Fig.3 shows the prevention values of each agricultural formulations at each concentration with respect to mildew of cucumber when the state of the disease is medium (200/leaf).
In this figure, O --- O, ~--- D and ~ --- ~ represent the coated NaHCO3 formulation, NaHCO3 formulation and aqueous solution of NaHCO3 respectively (Test Example 1).
As seen from the results shown in Fig. 3, the coated agricultural formulation of the present invention shows effects superior to those observed on the other agricultural chemicals.
Fig. 4 is a diagram illustrating the relationship between the prevention value and three different forms of the NaHCO3 formulation used while taking the state of generation of mildew of cucumber into consideration and changing the concentration as in Fig. 2.
The coated formulation of the invention can effectively sup~less the mildew of cucumber in severe state at each concentration e~Amined (250, 500 and 1,000 ppm) and ~ is found to be a preferred agricultural chemical. In this fig~-re, ~ , ~ , o / and ~ represent data corresponding to the number of spots due to disease of 40, 105, 200, 280, 510 ~and 975/leaf respectively. In addition, A, B and C are the same as those defined in Fig. 2.
Fig. 5 is a diagram illustrating the relationship between the prevention value of NaHCO3 formulations and the forms thereof used with respect to mildew of cucumber in severe state (the number of spots due to the disease:
450/leaf) while changing the concentration of the formulations. It is found that the coated formulation of the invention can effectively suppress the mildew of cucumber in severe state compared with aqueous solution and agricultural formulation of J.P. KOKAI No. 63-233902.
Fig. 6 shows the relation between the concentration of each agricultural formulation and the number of spots (phytotoxicity).
~ 334823 It is noted that unlike the conventional aqueous solution, the agricultural formulation of J.P. KOKAI No. 63-233902 and the coated formulation of the invention do not show phytotoxicity at a concentration of not more than 4,000 ppm.
AS dicussed above in detail, the coated agricultural formulation of the present invention exhibits the prevention - - value superio~ t~ thio~e of the uncoated a,gricult.u;r~
chemicals and the aforesaid agricultural formulations (J.P.
KOKAI No. 63-233902).
.If using an aqueous solution of conventional agricultural chemicals and the foregoing agricultural formulation, the number of spots due to disease in general increases and the prevention value thereof is lowered as the disease proceeds while the coated agricultural formulation of the invention does not show such tendency and shows stable efficiency.
The phytotoxicity of the coated formulation of the invention, which is estimated on the basis of the number of spots due to disease, is almost the same as that observed on the control (free from agricultural chemicals).
Claims (12)
1. A coated agricultural chemical comprising a powdery effective component of an agricultural chemical coated with at least one member selected from the group consisting of aliphatic acid esters of aliphatic polyols and phospholipids in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the effective-component.
2. A coated agricultural chemical of claim 1 wherein it further comprises spreading agents, wetting and spreading agents and/or anchorages.
3. A coated agricultural chemical of claim 1 wherein the aliphatic polyol moieties of the esters are selected from the group consiting of saturated and unsaturated aliphatic polyols having 3 to 6 carbon atoms and the aliphatic acid moieties of the esters are selected from the group consisting of saturated and unsaturated acids and mixture thereof.
4. A coated agricultural chemical of claim 3 wherein the aliphatic polyol moiety is glycerin, propylene glycol, sorbitol or sorbitan and the aliphatic acid moiety is selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, oleic acid, linolic acid, linolenic acid, ricinoleic acid, tallow, cottonseed oil, rapeseed oil and hardened oil.
5. A coated agricultural chemical of claim 1 wherein the ester is selected from the group consisting of sorbitan monolaurate, sorbitan monostearate, glycerin monooleate, glycerin monooctoate, glycerin mono-soyabeen oil fatty acid ester, glycerin mono-cottonseed oil fatty acid ester and polyglycerin fatty acid esters.
6. A coated agricultural chemical of claim 1 wherein the phospholipid is selected from the group consisting of phytolecithin derived from plant's oil, egg yolk; and phosphatidylcholine, phosphatidylethanolamine and phosphatidylinositol separated therefrom.
7. A coated agricultural chemical of claim 1 the effective component is in the form of solid powder at ordinary temperature.
8. A coated agricultural chemical of claim 7 wherein the effective component is water-soluble.
9. A coated agricultural chemical of claim 7 wherein the effective component is a member selected from the group consisting of copper 8-oxyquinoline, basic copper sulfate, basic copper chloride, copper(II) chloride, basic copper carbonate, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, antibiotic-polyoxin complex, o,o-diethyl-s-benzylthiophosphate, 2-sec-butylphenyl-N-methylcarbamate and o,o-dimethyl-2,2,2-trichloro-1-hydroxyethylphosphate; and sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, calcium carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium chloride, potassium chloride, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate.
10. A coated agricultural chemical of claim 1 wherein the particle size of the effective component is adjusted so that it passes through a sieve of 100 mesh.
11. A coated agricultural chemical of claim 10 wherein the particle size of the effective component is adjusted so that it passes through a sieve of 200 to 400 mesh.
12. A method of preventing or treating disease of a plant, comprising applying to the plant or its surroundings a solution containing a coated agricultural chemical as claimed in any one of claims 1 to 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62310497A JPH0764681B2 (en) | 1987-12-08 | 1987-12-08 | Pesticide coating agent |
| JP310497/1987 | 1987-12-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334823C true CA1334823C (en) | 1995-03-21 |
Family
ID=18005937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000585401A Expired - Lifetime CA1334823C (en) | 1987-12-08 | 1988-12-05 | Coated agricultural chemicals |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5123950A (en) |
| JP (1) | JPH0764681B2 (en) |
| KR (1) | KR910007354B1 (en) |
| CA (1) | CA1334823C (en) |
| FR (1) | FR2623973B1 (en) |
| GB (1) | GB2213378B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0764681B2 (en) * | 1987-12-08 | 1995-07-12 | 理化学研究所 | Pesticide coating agent |
| US5460817A (en) * | 1988-01-19 | 1995-10-24 | Allied Colloids Ltd. | Particulate composition comprising a core of matrix polymer with active ingredient distributed therein |
| AU3815993A (en) * | 1992-05-12 | 1993-12-13 | Church & Dwight Company, Inc. | Polyfunctional bicarbonate-containing agrochemical compositions |
| US5338551A (en) * | 1992-07-02 | 1994-08-16 | Lajoie M Stephen | Polyfunctional agrochemical bicarbonate-containing compositions |
| JP2711619B2 (en) * | 1992-07-23 | 1998-02-10 | 理化学研究所 | Sterilizing insecticidal composition |
| US5556631A (en) * | 1994-09-30 | 1996-09-17 | Kelley; Donald W. | Water resistant pesticide compositions |
| CN1241902A (en) | 1996-10-25 | 2000-01-19 | 孟山都公司 | Composition and method for treating plants with exogenous chemicals |
| CA2269631C (en) * | 1996-10-25 | 2008-03-25 | Monsanto Company | Composition and method for treating plants with exogenous chemicals |
| US5968222A (en) * | 1997-02-07 | 1999-10-19 | Cargill, Incorporated | Dust reduction agents for granular inorganic substances |
| JP3399789B2 (en) | 1997-07-15 | 2003-04-21 | 理化学研究所 | Plant disease control agent |
| WO1999055645A1 (en) * | 1998-04-29 | 1999-11-04 | Cognis Corporation | Agricultural adjuvant |
| AU2003202265A1 (en) * | 2002-01-09 | 2003-07-30 | Summerdale, Inc. | Fungicide compositions |
| KR100468002B1 (en) * | 2002-02-19 | 2005-01-24 | 이수양 | The manufacturing method of a herbicidal composition comprising mainly salt for grass-protection |
| US7820594B2 (en) * | 2003-01-09 | 2010-10-26 | Coleman Robert D | Pesticide compositions and methods for their use |
| WO2006014462A2 (en) * | 2004-07-06 | 2006-02-09 | Pharm Solutions, Inc. | Multifunctional compositions having combined insecticidal, mitacidal and fungicidal activity |
| WO2012048170A2 (en) | 2010-10-06 | 2012-04-12 | Massachusetts Institute Of Technology | Humanized animals via tissue engineering and uses therefor |
| CA2812193C (en) * | 2010-10-18 | 2017-09-26 | Tiger-Sul Products Llc | Coated fertilizer particles |
| US9137991B1 (en) * | 2012-01-26 | 2015-09-22 | Floratine Products Group, Inc. | Choline containing composition and method of use |
| WO2014011775A1 (en) | 2012-07-10 | 2014-01-16 | The Trustees Of The University Of Pennsylvania | Biomaterials for enhanced implant-host integration |
| US11338065B2 (en) | 2015-10-08 | 2022-05-24 | Massachusetts Institute Of Technology | In situ expansion of engineered devices for regeneration |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3706545A (en) * | 1970-08-27 | 1972-12-19 | Itt | Foliar sprays |
| US3799755A (en) * | 1971-01-12 | 1974-03-26 | D Rack | Process for the manufacture of a plant substrate body |
| US4394149A (en) * | 1978-02-24 | 1983-07-19 | Szoka Jr Francis C | Plant nutriment compositions and method of their application |
| JPS5511556A (en) * | 1978-07-13 | 1980-01-26 | Rikagaku Kenkyusho | Bactericidal agent for agriculture and horticulture |
| GB2075344A (en) * | 1980-04-21 | 1981-11-18 | Stauffer Chemical Co | Slow release herbicide granules |
| DE3029159A1 (en) * | 1980-08-01 | 1982-02-25 | Sandvik Conveyor Gmbh, 7012 Fellbach | Dough pieces transfer installation - esp. preformed doughy material moved to conveyor band on a rotatable table equipped with swivel plates |
| DE3226147A1 (en) * | 1982-07-13 | 1984-01-19 | A. Nattermann & Cie GmbH, 5000 Köln | Method for encapsulating biocidal active substances |
| JPS5955804A (en) * | 1982-09-22 | 1984-03-31 | ア−・ナツタ−マン・ウント・シ−・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Fungicide composition |
| JPS5955803A (en) * | 1982-09-22 | 1984-03-31 | ア−・ナツタ−マン・ウント・シ−・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Nematocide composition |
| JPH0764681B2 (en) * | 1987-12-08 | 1995-07-12 | 理化学研究所 | Pesticide coating agent |
-
1987
- 1987-12-08 JP JP62310497A patent/JPH0764681B2/en not_active Expired - Lifetime
-
1988
- 1988-12-05 CA CA000585401A patent/CA1334823C/en not_active Expired - Lifetime
- 1988-12-08 KR KR1019880016341A patent/KR910007354B1/en not_active IP Right Cessation
- 1988-12-08 GB GB8828682A patent/GB2213378B/en not_active Expired - Lifetime
- 1988-12-08 FR FR8816148A patent/FR2623973B1/en not_active Expired - Lifetime
-
1990
- 1990-04-04 US US07/504,009 patent/US5123950A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0764681B2 (en) | 1995-07-12 |
| GB2213378A (en) | 1989-08-16 |
| KR910007354B1 (en) | 1991-09-25 |
| GB2213378B (en) | 1991-08-14 |
| JPH01151501A (en) | 1989-06-14 |
| GB8828682D0 (en) | 1989-01-11 |
| KR890009267A (en) | 1989-08-01 |
| US5123950A (en) | 1992-06-23 |
| FR2623973B1 (en) | 1993-10-08 |
| FR2623973A1 (en) | 1989-06-09 |
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