CA1226211A - Fungicidal formulations - Google Patents
Fungicidal formulationsInfo
- Publication number
- CA1226211A CA1226211A CA000433070A CA433070A CA1226211A CA 1226211 A CA1226211 A CA 1226211A CA 000433070 A CA000433070 A CA 000433070A CA 433070 A CA433070 A CA 433070A CA 1226211 A CA1226211 A CA 1226211A
- Authority
- CA
- Canada
- Prior art keywords
- selfware
- formula
- formulation
- formulations
- fungicidal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
-
- 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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Chemical & Material Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE INVENTION
FUNGICIDAL FORMULATIONS
The invention provides a fungicidal formulation comprising sulphur and a compound of formula
FUNGICIDAL FORMULATIONS
The invention provides a fungicidal formulation comprising sulphur and a compound of formula
Description
- ~LZ26~
FU~GICIDAL FORMULATIONS
This invention relates to fungicidal formulations and to methods of treating finagle infections of cultivated plants.
the invention provides a fungicidal formulation comprising Selfware and a pyrimidine of formula I
Of (I) ,,~
it where X is chlorine or fluorine.
We have discovered that this combination of ingredients is specially effective in controlling or combating finagle infections of cultivated plants such as vines, top fruit and vegetables. These mixtures have been found to give good results against powdery mildew Uncinula negator on vines, Podosphaera leucotricha on apples, and Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits. The compounds of formula (I) are known fungicides described, for example, in British Patent 1 218 623, and their effectiveness is surprisingly improved by the presence or Selfware.
Sicily Accordingly the invention also includes a method of treating finagle infections of plants which comprises applying to the plants a fungicidally effective amount of a fungicidal formulation as defined above. The formulation is preferably applied by fuller application at any time before harvest of the crop. The amount and frequency of application will depend on the severity of the finagle disease and the condition of the crop. It has, however, been found that the frequency of treatment needed for finagle control can be reduced by the use of the formulation of the invention, and a valuable reduction in labor cost is achieved thereby.
With regard to the amount of the active ingredients to be employed, it is preferred to apply a fuller spray in which the Selfware is applied at a rate of from 1000 to 5000 g per Hector, and the component of formula (I) at a rate of from 5 to 100 g per Hector. The ratio of Selfware and compounds of formula (I) is preferably from 1:1 or 10:1 to 1000:1, for example, from 10:1 to 500:1, such as from 50:1 to 500 1.
The Selfware component in the formulation of the invention may be in any of the convenient forms which allow satisfactory formulation with the compounds of formula (I), being preferably either micronised Selfware or colloidal Selfware, and the mean particle size of the end product is preferably between 1 and 20 microns. Of the two active compounds comprised by formula (I) above, fenarimol, the compound in which X is chlorine is preferred, though normal (X is fluorine) can equally be used. As noted above both compounds are well known in the fungicide art and can be employed with other compatible fungicides, although generally they are, together with Selfware, the sole active ingredients of the formulation.
~L~Z~i2~L
The formulation of the invention will usually be associated with one or more inert, non-phytotoxic carrier sand it is to be understood that the formulation can also include additional fungicide ingredients. In order to simplify manufacture, storage and transport, combinations are normally produced in concentrate form intended for dilution in water to the degree necessary to give the above mentioned application rates. Such concentrated formulations may contain from 0.5 to 90%, preferably from 5% to 90%, by weight of active ingredients associated with an inert non-phytotoxic carrier. Such formulations will usually be in the form ox a wettable powder, dispersible granules or a suspension concentrate.
The concentrate formulations are intended for dilution with water or other suitable substances prior to use in conventional spray tanks or for aerial application and it is to be understood that the diluted formulations so produced are formulations in accordance with the invention in which the inert non-phytotoxic carrier is water or other suitable substance.
Wettable powders comprise an intimate mixture of the active ingredients, an inert carrier and an appropriate surfactant.
The inert carrier may be chosen from for example alumina, a~tapulgite clays, montmorillonite clays, diatom~ceous earths, precipitated silica, kaolin, micas, talcs and purified silicates. Effective surfactants can be selected from sulfonated lignins, naphthalene sulfonates and condensed naphthalene sulfonates, alkyd succinates, alkylbenzene sulfonates, alkyd sulfites and non ionic surfactants such as alkyd or aureole initiated ethylene oxide adduces for example ethylene oxide adduces of phenol. Examples of wettable powders are those having the following composition:
1226Z~
Wettable Powder _ % by weight Formula I compound to 2.5 Selfware 40 to 90 Surfactants 4 to 10 Anti caking agent to 15 Inert carrier to 100 Suspension concentrates comprise a suspension of the active ingredients, a surfactant, a suspending agent and water or a non-aqueous medium. Examples of suspension concentrates comprise the active ingredients and for example, surfactants, suspending agent, anti foaming agent, anti freezing agent and water, for example:
Suspension Concentrates % by weight Formula 1 compound to 2.5 Selfware 40 to 80.
Suspending agent to 10 Surfactants 1 to 5 Anti foam 0.1 to 1.0 Antifreeze 5 to 20 Water to 100 Examples of dispersible granules are those having the following composition:
~2262~
Dispersible Granules % by Weight Formula I compound 0.1 to 2.5 Selfware 40 to 80 Surfactants .4 to 15 Anti caking agent 0 to 10 Binder 0 to 10 Disintegrant 0 to 10 Inert carrier to 100 The invention also includes a method of preparing the preferred wettable powder formulation comprising as active ingredients Selfware and a pyrimidine of formula (I) above, which comprises blending the active ingredients with excipients and milling the blend to give the requisite particle size, preferably being a mean particle size of between 1 and 20 microns.
The pyrimidine of formula (I) in which X is chlorine is known as fenarimol and is available from Eli Lilly and Company as for example'Bloc','Rimidin' and'Rubigan" and the compound of formula (I) in which X is fluorine is known as normal, available from the same company as, for example "Trimidal"and"Trimino~'.
The following Examples illustrate the invention:
1. Trademark
FU~GICIDAL FORMULATIONS
This invention relates to fungicidal formulations and to methods of treating finagle infections of cultivated plants.
the invention provides a fungicidal formulation comprising Selfware and a pyrimidine of formula I
Of (I) ,,~
it where X is chlorine or fluorine.
We have discovered that this combination of ingredients is specially effective in controlling or combating finagle infections of cultivated plants such as vines, top fruit and vegetables. These mixtures have been found to give good results against powdery mildew Uncinula negator on vines, Podosphaera leucotricha on apples, and Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits. The compounds of formula (I) are known fungicides described, for example, in British Patent 1 218 623, and their effectiveness is surprisingly improved by the presence or Selfware.
Sicily Accordingly the invention also includes a method of treating finagle infections of plants which comprises applying to the plants a fungicidally effective amount of a fungicidal formulation as defined above. The formulation is preferably applied by fuller application at any time before harvest of the crop. The amount and frequency of application will depend on the severity of the finagle disease and the condition of the crop. It has, however, been found that the frequency of treatment needed for finagle control can be reduced by the use of the formulation of the invention, and a valuable reduction in labor cost is achieved thereby.
With regard to the amount of the active ingredients to be employed, it is preferred to apply a fuller spray in which the Selfware is applied at a rate of from 1000 to 5000 g per Hector, and the component of formula (I) at a rate of from 5 to 100 g per Hector. The ratio of Selfware and compounds of formula (I) is preferably from 1:1 or 10:1 to 1000:1, for example, from 10:1 to 500:1, such as from 50:1 to 500 1.
The Selfware component in the formulation of the invention may be in any of the convenient forms which allow satisfactory formulation with the compounds of formula (I), being preferably either micronised Selfware or colloidal Selfware, and the mean particle size of the end product is preferably between 1 and 20 microns. Of the two active compounds comprised by formula (I) above, fenarimol, the compound in which X is chlorine is preferred, though normal (X is fluorine) can equally be used. As noted above both compounds are well known in the fungicide art and can be employed with other compatible fungicides, although generally they are, together with Selfware, the sole active ingredients of the formulation.
~L~Z~i2~L
The formulation of the invention will usually be associated with one or more inert, non-phytotoxic carrier sand it is to be understood that the formulation can also include additional fungicide ingredients. In order to simplify manufacture, storage and transport, combinations are normally produced in concentrate form intended for dilution in water to the degree necessary to give the above mentioned application rates. Such concentrated formulations may contain from 0.5 to 90%, preferably from 5% to 90%, by weight of active ingredients associated with an inert non-phytotoxic carrier. Such formulations will usually be in the form ox a wettable powder, dispersible granules or a suspension concentrate.
The concentrate formulations are intended for dilution with water or other suitable substances prior to use in conventional spray tanks or for aerial application and it is to be understood that the diluted formulations so produced are formulations in accordance with the invention in which the inert non-phytotoxic carrier is water or other suitable substance.
Wettable powders comprise an intimate mixture of the active ingredients, an inert carrier and an appropriate surfactant.
The inert carrier may be chosen from for example alumina, a~tapulgite clays, montmorillonite clays, diatom~ceous earths, precipitated silica, kaolin, micas, talcs and purified silicates. Effective surfactants can be selected from sulfonated lignins, naphthalene sulfonates and condensed naphthalene sulfonates, alkyd succinates, alkylbenzene sulfonates, alkyd sulfites and non ionic surfactants such as alkyd or aureole initiated ethylene oxide adduces for example ethylene oxide adduces of phenol. Examples of wettable powders are those having the following composition:
1226Z~
Wettable Powder _ % by weight Formula I compound to 2.5 Selfware 40 to 90 Surfactants 4 to 10 Anti caking agent to 15 Inert carrier to 100 Suspension concentrates comprise a suspension of the active ingredients, a surfactant, a suspending agent and water or a non-aqueous medium. Examples of suspension concentrates comprise the active ingredients and for example, surfactants, suspending agent, anti foaming agent, anti freezing agent and water, for example:
Suspension Concentrates % by weight Formula 1 compound to 2.5 Selfware 40 to 80.
Suspending agent to 10 Surfactants 1 to 5 Anti foam 0.1 to 1.0 Antifreeze 5 to 20 Water to 100 Examples of dispersible granules are those having the following composition:
~2262~
Dispersible Granules % by Weight Formula I compound 0.1 to 2.5 Selfware 40 to 80 Surfactants .4 to 15 Anti caking agent 0 to 10 Binder 0 to 10 Disintegrant 0 to 10 Inert carrier to 100 The invention also includes a method of preparing the preferred wettable powder formulation comprising as active ingredients Selfware and a pyrimidine of formula (I) above, which comprises blending the active ingredients with excipients and milling the blend to give the requisite particle size, preferably being a mean particle size of between 1 and 20 microns.
The pyrimidine of formula (I) in which X is chlorine is known as fenarimol and is available from Eli Lilly and Company as for example'Bloc','Rimidin' and'Rubigan" and the compound of formula (I) in which X is fluorine is known as normal, available from the same company as, for example "Trimidal"and"Trimino~'.
The following Examples illustrate the invention:
1. Trademark
2. "
3. 'I
4. "
5. "
~ZZ6~
The following wettable powder was prepared:
% by weight Fenarimol or normal 0.5 Selfware I
Alkyd naphthalene sulphonatP 3 Sulphonated raft sulphonate 3 Silicon dioxide 3 Kaolin to 100 The active ingredients were blended with the specie fled excipients in conventional mixing equipment. The blend was then milled in a fluid energy mill to a particle size distribution range of from 0 to 10 microns and finally the mixture was reblended and darted prior to being packaged.
-The following suspension concentrate was prepared:
% by weight Fenarimol or normal 0.5 Selfware 80 Polyaryl exulted phosphate 3 ~aphthalene formaldehyde condensate 3 Ethylene glycol 5 Silicone emulsion I
Xanthan gum 0.2 Water to 100 1;~26~
Top ingredients (with the exception of the suspending agent) were blended with part of the liquid phase and the slurry milled to a fine particle size of 0 to 10 microns. A
gel comprising the suspending agent and remainder of the liquid phase was prepared and then mixed with the milled slurry to give the product.
The following dispersible granule composition was prepared:
lo by weight Fenarimol or normal%
Selfware 80%
Alkyd laureate 3%
Sodium phenol sulphonate 5%
Alginic acid 5%
Kaolin to 100 The ingredients were mixed and milled in a fluid energy mill to a size range of 0 to lo microns and granulated.
The following example illustrates the synergistic properties of the formulations of the invention.
Following intensive use of fenarimol over several years strains of Sphaerotheca fuliginea have developed which are less sensitive to fenarimol. Such strains were used in the following greenhouse experiment.
Cucumber plants at the one true leaf stage and contained in individual pots, were sprayed with aqueous suspension of Selfware, fenarimol and sulphur/fenarimol mixtures.
issue 24 Hours after spraying, when the spray had thoroughly dried on the leaf surface, the leaf was inoculated with Sphaerotheca fuliginea. After a lapse of ten days the percentage finagle control was measured in relation to control plants which had not been treated with fungicide components, and the following results were obtained.
Selfware Pam ~enarimol (Pam) 0 50 100 When analyzed by the well known "Colby equation" (see 15 Weeds, 15, 20-22 (1967)) the above results clearly demonstrated synergism under the conditions of the test.
~ZZ6~
The following wettable powder was prepared:
% by weight Fenarimol or normal 0.5 Selfware I
Alkyd naphthalene sulphonatP 3 Sulphonated raft sulphonate 3 Silicon dioxide 3 Kaolin to 100 The active ingredients were blended with the specie fled excipients in conventional mixing equipment. The blend was then milled in a fluid energy mill to a particle size distribution range of from 0 to 10 microns and finally the mixture was reblended and darted prior to being packaged.
-The following suspension concentrate was prepared:
% by weight Fenarimol or normal 0.5 Selfware 80 Polyaryl exulted phosphate 3 ~aphthalene formaldehyde condensate 3 Ethylene glycol 5 Silicone emulsion I
Xanthan gum 0.2 Water to 100 1;~26~
Top ingredients (with the exception of the suspending agent) were blended with part of the liquid phase and the slurry milled to a fine particle size of 0 to 10 microns. A
gel comprising the suspending agent and remainder of the liquid phase was prepared and then mixed with the milled slurry to give the product.
The following dispersible granule composition was prepared:
lo by weight Fenarimol or normal%
Selfware 80%
Alkyd laureate 3%
Sodium phenol sulphonate 5%
Alginic acid 5%
Kaolin to 100 The ingredients were mixed and milled in a fluid energy mill to a size range of 0 to lo microns and granulated.
The following example illustrates the synergistic properties of the formulations of the invention.
Following intensive use of fenarimol over several years strains of Sphaerotheca fuliginea have developed which are less sensitive to fenarimol. Such strains were used in the following greenhouse experiment.
Cucumber plants at the one true leaf stage and contained in individual pots, were sprayed with aqueous suspension of Selfware, fenarimol and sulphur/fenarimol mixtures.
issue 24 Hours after spraying, when the spray had thoroughly dried on the leaf surface, the leaf was inoculated with Sphaerotheca fuliginea. After a lapse of ten days the percentage finagle control was measured in relation to control plants which had not been treated with fungicide components, and the following results were obtained.
Selfware Pam ~enarimol (Pam) 0 50 100 When analyzed by the well known "Colby equation" (see 15 Weeds, 15, 20-22 (1967)) the above results clearly demonstrated synergism under the conditions of the test.
Claims (5)
1. A fungicidal formulation comprising sulphur and a compound of formula (I) where X is chlorine or fluorine.
2. A formulation according to claim 1 in which the ratio of sulphur to compound of formula (I) is in the range of from 10:1 to 500:1.
3. A formulation according to either of claims 1 and 2 wherein the sulphur is micronised sulphur.
4. A method of treating fungal infections of plants which comprises applying to the plants a fungicidal formulation as defined in claim 1.
5. A method of treating vines according to claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8221925 | 1982-07-29 | ||
| GB8221925 | 1982-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1226211A true CA1226211A (en) | 1987-09-01 |
Family
ID=10531988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000433070A Expired CA1226211A (en) | 1982-07-29 | 1983-07-25 | Fungicidal formulations |
Country Status (34)
| Country | Link |
|---|---|
| JP (1) | JPS5942309A (en) |
| KR (1) | KR890002008B1 (en) |
| AT (1) | AT385177B (en) |
| AU (1) | AU562787B2 (en) |
| BE (1) | BE897427A (en) |
| BG (1) | BG36492A3 (en) |
| BR (1) | BR8304002A (en) |
| CA (1) | CA1226211A (en) |
| CH (1) | CH657751A5 (en) |
| CS (1) | CS238644B2 (en) |
| DD (1) | DD209958A5 (en) |
| DE (1) | DE3326664A1 (en) |
| DK (1) | DK158762C (en) |
| DZ (1) | DZ563A1 (en) |
| EG (1) | EG17915A (en) |
| ES (1) | ES524467A0 (en) |
| FR (1) | FR2530925B1 (en) |
| GR (1) | GR77585B (en) |
| HU (1) | HU188934B (en) |
| IE (1) | IE55535B1 (en) |
| IL (1) | IL69344A0 (en) |
| IT (1) | IT1173747B (en) |
| LU (1) | LU84937A1 (en) |
| MA (1) | MA19859A1 (en) |
| NL (1) | NL8302646A (en) |
| NZ (1) | NZ205022A (en) |
| PL (1) | PL136648B1 (en) |
| PT (1) | PT77101B (en) |
| RO (2) | RO91475A (en) |
| SE (1) | SE453956B (en) |
| SU (1) | SU1272965A3 (en) |
| TR (1) | TR21840A (en) |
| UA (1) | UA6334A1 (en) |
| ZA (1) | ZA835494B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101500584B (en) * | 2006-06-02 | 2012-12-12 | 奈彻若Ma公司 | Use of micron sulfur in prevention and treatment for pathogenic disorder of human or animal |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2502971B2 (en) * | 1985-11-09 | 1996-05-29 | カシオ計算機株式会社 | Character output device |
| JPS62182978A (en) * | 1986-02-07 | 1987-08-11 | Sanyo Electric Co Ltd | Pattern enlarging method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1569940A (en) * | 1967-04-27 | 1969-06-06 | ||
| CS217978B2 (en) * | 1978-04-01 | 1983-02-25 | Lilly Industries Ltd | Fungicide means |
-
1983
- 1983-07-23 DE DE19833326664 patent/DE3326664A1/en active Granted
- 1983-07-24 EG EG447/83A patent/EG17915A/en active
- 1983-07-25 JP JP58136669A patent/JPS5942309A/en active Granted
- 1983-07-25 RO RO83118982A patent/RO91475A/en unknown
- 1983-07-25 GR GR72023A patent/GR77585B/el unknown
- 1983-07-25 AU AU17242/83A patent/AU562787B2/en not_active Ceased
- 1983-07-25 FR FR8312261A patent/FR2530925B1/en not_active Expired
- 1983-07-25 CH CH4055/83A patent/CH657751A5/en not_active IP Right Cessation
- 1983-07-25 CA CA000433070A patent/CA1226211A/en not_active Expired
- 1983-07-25 RO RO83111715A patent/RO88234A/en unknown
- 1983-07-26 NZ NZ205022A patent/NZ205022A/en unknown
- 1983-07-26 NL NL8302646A patent/NL8302646A/en not_active Application Discontinuation
- 1983-07-26 KR KR1019830003472A patent/KR890002008B1/en not_active IP Right Cessation
- 1983-07-26 TR TR21840A patent/TR21840A/en unknown
- 1983-07-26 DD DD83253416A patent/DD209958A5/en not_active IP Right Cessation
- 1983-07-26 AT AT0271483A patent/AT385177B/en not_active IP Right Cessation
- 1983-07-26 PT PT77101A patent/PT77101B/en unknown
- 1983-07-26 IL IL69344A patent/IL69344A0/en not_active IP Right Cessation
- 1983-07-27 IT IT48756/83A patent/IT1173747B/en active
- 1983-07-27 DZ DZ836912A patent/DZ563A1/en active
- 1983-07-27 ES ES524467A patent/ES524467A0/en active Granted
- 1983-07-27 BR BR8304002A patent/BR8304002A/en not_active IP Right Cessation
- 1983-07-27 SE SE8304162A patent/SE453956B/en not_active IP Right Cessation
- 1983-07-27 PL PL1983243197A patent/PL136648B1/en unknown
- 1983-07-27 ZA ZA835494A patent/ZA835494B/en unknown
- 1983-07-27 IE IE1776/83A patent/IE55535B1/en not_active IP Right Cessation
- 1983-07-28 UA UA3622801A patent/UA6334A1/en unknown
- 1983-07-28 DK DK346883A patent/DK158762C/en not_active IP Right Cessation
- 1983-07-28 HU HU832659A patent/HU188934B/en not_active IP Right Cessation
- 1983-07-28 MA MA20080A patent/MA19859A1/en unknown
- 1983-07-28 CS CS835659A patent/CS238644B2/en unknown
- 1983-07-28 BG BG061919A patent/BG36492A3/en unknown
- 1983-07-28 SU SU3622801A patent/SU1272965A3/en active
- 1983-07-29 BE BE6/47857A patent/BE897427A/en not_active IP Right Cessation
- 1983-07-29 LU LU84937A patent/LU84937A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101500584B (en) * | 2006-06-02 | 2012-12-12 | 奈彻若Ma公司 | Use of micron sulfur in prevention and treatment for pathogenic disorder of human or animal |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |