WO1995028840A1 - Hydrogen peroxide composition formulated for the preventive and curative treatment of diseases affecting the foliage and aerial parts of plants - Google Patents

Hydrogen peroxide composition formulated for the preventive and curative treatment of diseases affecting the foliage and aerial parts of plants Download PDF

Info

Publication number
WO1995028840A1
WO1995028840A1 PCT/FR1995/000516 FR9500516W WO9528840A1 WO 1995028840 A1 WO1995028840 A1 WO 1995028840A1 FR 9500516 W FR9500516 W FR 9500516W WO 9528840 A1 WO9528840 A1 WO 9528840A1
Authority
WO
WIPO (PCT)
Prior art keywords
agent
composition according
hydrogen peroxide
derivatives
acid
Prior art date
Application number
PCT/FR1995/000516
Other languages
French (fr)
Inventor
Jean-Louis Soyez
Original Assignee
Soyez, Anne
Soyez, Jean-Eric
Soyez, Marie-Laure
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Soyez, Anne, Soyez, Jean-Eric, Soyez, Marie-Laure filed Critical Soyez, Anne
Publication of WO1995028840A1 publication Critical patent/WO1995028840A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

Definitions

  • Composition based on hydrogen peroxide formulated for the preventive and curative treatment of leaf and air diseases of plants.
  • Hydrogen peroxide has also been used in agriculture, in applications relating to the bactericidal role which is recognized in the medical field. It has thus been studied as such in the treatment of seeds or fruits after harvest, but also in combination with other compounds in the fight against parasitic fungi of plants.
  • the document JP-5 229 910 discloses the combination of hydrogen peroxide with an antimicrobial agent effective against Plasmodiophora brassicae, the fungus responsible for the hernia of cabbage; and document US-A-5,079,868 discloses the combination of hydrogen peroxide with urea to fight in particular against Peronospora and Phytophtora, two fungi affecting the vine. Hydrogen peroxide has also been used alone for this type of application.
  • European patent application EP-A-0 347 731 discloses a process for combating plant bacteria and parasites, and in particular Botrytis, oidium and downy mildew, which consists of spraying, after the start of infection, on the aerial parts of plants, a solution containing 0.05 to 5% by weight of 35% hydrogen peroxide, possibly associated with compounds believed to enhance the fight against parasites, such as calcium compounds, and / or compounds promoting plant growth, such as magnesium compounds, and / or organic peracids and / or sulfur.
  • the major drawback of this known process is that the quantities of sprayed hydrogen peroxide, except in the particular case of inflorescence botrytis, range from 19.5 to 45 l / ha, the preferred quantities being close to 19, 5 to 30 1 / ha, that is to say much higher than the limits acceptable in phytosanitary practice, which must remain, at best, less than 5 1 / ha and, in any case, below 10 1 / ha to reduce as much as possible the quantities of product to be transported to the place of treatment.
  • the invention solves this problem by proposing a new specific formulation based on hydrogen peroxide which makes it possible to fight effectively against pathogenic fungi parasites of the aerial parts of plants, and in particular of the vine, a contact sporicide-fungicide constituted by said formulation, as well as a method of combating such fungi, which consists in spraying said formulation or said sporicide-fungicide on plants.
  • the particular formulation of the invention has an effectiveness such that the application of a quantity of hydrogen peroxide per hectare much lower than that sprayed according to the prior art makes it possible to destroy the fungi and spores (5 1 / ha of the proposed formulation, with extreme values ranging from 2 to 10 1 / ha). More specifically, the subject of the invention is:
  • compositions for the preventive and curative treatment of leaf and air diseases of plants comprising: a) hydrogen peroxide; b) at least one surfactant; c) at least one peroxide stabilizing agent; d) at least one agent delaying evaporation; e) at least one tackifier; f) at least one anti-corrosion agent, which composition provides, at the time of use, from 10 to 20,000 ppm of hydrogen peroxide; and
  • alcohols monalcohols, such as methanol, propanol, butanol; ethylene glycol; polyglycols, such as poly (ethylene glycol), and their esters; poly-glycerols and their fatty acid monoesters, sorbitol; oxyethylenic and oxypropylenic derivatives, such as mono- or di-esters of fatty acids; polyoxyethylene and polyoxypropylene ethers of fatty alcohols or acid-alcohols; mercaptan ethers; oxyethylene and oxypropylene derivatives of amines or amides of amino alcohols; al ylarylpolyal yleneoxide derivatives; fatty ester derivatives, such as derivatives of the polyol esters of sucrose, of sorbitol; and (poly) oxyethylene and (poly) oxypropylene ethers of
  • These surface active agents represent from about 0.05 to about 2% by weight of the formulation. They can be used alone or in combination. These compounds are available from a variety of suppliers, for example from BASF under the names PLURONIC R and TETRONIC R , from ICI under the name ATPLUS R , from RHONE-POULENC under the names RHODAMINE R , IGEPAL R , ALKAMUL R and ANTAR0X R , with O NICHEM under the name TENSIOFIX R , with UNION CARBIDE under the name TERGITOL R.
  • the formulation also contains from about 1 to about 5% by weight of at least one peroxide stabilizing agent, such as benzenesulfonic acid, trifluoroacetic acid, hydrochloric acid, nitric acid. , phosphoric acid and sulfuric acid, used alone or in combination, which are commonly available commercially.
  • the formulation also contains from 0.05 to about 1% of at least one anti-corrosion agent and / or of one or more sequestrants, such as benzotriazole and / or ethylene diamine tetraacetic acid (EDTA).
  • evaporation delaying agents intended to prevent the formulation from evaporating when sprayed on the plant and to reduce the rate of decomposition of the active ingredient applied to the plant, it is possible to use from about 0.1 to about 5% either of one or more alcohols, such as glycol or isopropanol, or of hexanedioic acid, or of a mixture of these.
  • Tack improving agents or reducing rain leaching which can be used in the present invention include from about 0.1 to about 0.5% of pyrrolidone derivatives, such as, for example, AGRIMAX R , AGRISYNTH R or AGRIMER R , which are available from ISP.
  • pyrrolidone derivatives such as, for example, AGRIMAX R , AGRISYNTH R or AGRIMER R , which are available from ISP.
  • the formulation according to the invention can also comprise compounds which have no influence on the effectiveness of the invention but are intended to warn the manipulator, such as dyes soluble in water (ACID RED, YELLOW SULPHONE , etc.) and / or odorants (olfactory denaturants) present up to about 5% by weight in the formulation (acetic acid, propionic acid, heptanoic acid or picric acid, for example, used alone or in combination).
  • dyes soluble in water ACID RED, YELLOW SULPHONE , etc.
  • odorants olfactory denaturants
  • the formulation also contains one or more compatible fungicides chosen from sulfur, benzimidazoles, dithiocarbamates, phenol derivatives, phthaliides, cyclic imides, amine derivatives. amides, diazine derivatives, morpholine heterocycles, imidazoles and triazoles.
  • the formulation provides, at the time of use, from 500 to 5,000 ppm of hydrogen peroxide and a conventional concentration, or possibly reduced, of said fungicide (s). It was noted that the combination of the formulated hydrogen peroxide with another fungicide could have a synergistic effect.
  • Formulation B hydrogen peroxide 32.5% wetting agent: alkylphenolethoxylate 0.5% acid stabilizer and anti ⁇ corrosion: EDTA / nitric acid mixture 10/90 1.5% agents delaying evaporation and improving adhesiveness: alcohols / PVP 0.5% dye: ACID RED 0.10% odor denaturant: picric acid 0.10% water qs 100%
  • Formulation C once diluted in distilled water to reduce the hydrogen peroxide concentration to 32.5%, will be designated by MRA in the following description. It is understood, however, that the formulations according to the invention may be more diluted, depending on the objective sought, and, ultimately, these formulations may contain from 20 to 32.5% of hydrogen peroxide, with correlative variations of formulating agents.
  • the subject of the invention is also a process for the preventive or curative treatment of leaf and air diseases of plants, which consists in spraying on plants 50 to 400 l / ha, but preferably 100 to 250 l / ha, of the sporicide -fungicide or of the formulation defined in general terms above, or else a process which consists in subjecting said plants jointly to a treatment using said formulation, which provides, at the time of use, between 500 ppm and 5000 ppm of hydrogen peroxide and is applied at a rate of 50 to 400 l / ha, and to a treatment using one or more fungicides chosen from sulfur, benzimidazoles, dithiocarbamates, phenol derivatives, phthalides, cyclic imides, amine-amide derivatives, diazine derivatives, morpholine heterocycles, imidazoles and triazoles and phosethyl-Al.
  • fungicides chosen from sulfur, benzimidazoles, dithiocarbamates, phenol derivatives,
  • hydrogen peroxide concentrations indicated above correspond to volume or weight fractions of a formulation which is then applied in 50 to 400 liters of spray mixture per hectare.
  • 20,000 ppm or 2% of formulation in 400 l / ha of spray solution corresponds to 8 l / ha of sprayed formulated product.
  • the diseases susceptible to a sporicidal-fungicidal treatment by the formulation according to the invention are those where, at one stage or another, spores and / or mycelia have developed on the surface of the aerial organs of the plant. These diseases can be:
  • Oocetes Pythium, Phytophtora, Plasmopara, Peronospora, Bremia and Albugo;
  • Basidiomycetes Ustilago, Tilletia, Urocystis, Uro yces, Puccinia, Tranzchelia, Phragmidium, Gymnosporangium, Melampsora, Rhizoctonia, Stereu, Typhula, Phellinus;
  • Adelomycetes Pho a, Phyllosticta, Aschochyta, Septoria, Fusicoccum, Coniothyrium, Gleosporium,
  • the formulation according to the invention can be used in sprayers suitable for reaching the diseased part of the plant: either alone (if the harvest is approaching, for example, and the objective sought is efficiency with no residue on the crop), or extemporaneously in addition to appropriate organic fungicides chosen from the following families.
  • benzimidazoles such as carbendazim.
  • dithiocarbamates such as mancozebe and thiurame.
  • certain phenol derivatives such as dinocap
  • phthalimides such as phaltane and captan.
  • cyclic imides such as iprodione.
  • amine-amide derivatives such as cymoxanil, metalaxyl, ofurace.
  • diazine derivatives such as nuarimol,.
  • morpholine heterocycles (fenpropemorph) imidazoles (prochloraze) triazoles (triadimephon)
  • Botrytis cinerea For this purpose, an S9 strain of Botrytis cinerea on a vine and kept in a 2% CRISTOMAT-agar liquid nutrient medium in Petri dishes, at a temperature of 19 ° C and in the dark.
  • the assay was performed on a 24-well cell culture plate. 1.5 ml of distilled water was added to each well, supplemented with either MB or MRA, at concentrations of 0; 0.002; 0.005; 0.01 and 0.02% by weight. Then added 50 ⁇ l of conidia suspension, at 10 5 spores / ml, to each well. The germination of the conidia was evaluated after 24 hours of incubation at 19 ° C. The results are presented in Table 1 where DE 50 and DE 95 represent the effective dose for destroying 50% and 95% of the conidia population respectively.
  • the product MB and the formulation MRA were used at concentrations of 0.002; 0.02; 0.2 and 2%.
  • Each Petri dish containing 20 ml of DIAMALT-Agar was seeded in the center with a growing mycelial implant, 4 mm in diameter.
  • isolate 1519 appears less sensitive than isolate 1097 to the two preparations, it is deduced from these results that the MRA formulation is approximately 1.8 to 2 times more active than the product MB (peroxide concentration about 1.8 to 2 times lower for the same result).
  • a comparative test was carried out between the MRA formulation and a vinchlozoline preparation (used as a reference treatment), applied to the Pinot noir grape variety, in Champagne, in Aube.
  • Four repetitions were carried out (on four different plots) of the same test, which consisted of spraying 400 1 / ha of the MRA formulation diluted up to 2% (ie 8 1 / ha of MRA), at the classic phenological stages D (3 weeks before harvest) and D + 8 (8 days later).
  • TNT An untreated control (TNT) was also evaluated. The results recorded at the time of harvest are given in Table 4.
  • a comparative test was carried out between the MRA formulation and wettable sulfur (that is to say a ' sprayable powder consisting of sulfur with wetting agent) in Roussillon, at Sainte-Colombe, on a Syrah grape.
  • wettable sulfur that is to say a ' sprayable powder consisting of sulfur with wetting agent
  • Wettable sulfur THIOVIT supplied by SANDOZ, was tested in parallel, also at the rate of 6 sprays of 12.5 kg / ha. An untreated control (TNT) was also evaluated.
  • TNT untreated control
  • Monilia (responsible for moniliosis), Botrytis (responsible for botrytis or rot), Erysiphe (responsible for powdery mildew in cereals) and Septoria nodorum (responsible for septoria blight in cereals), only in the vineyard, in tests on: Botrytis , Plasmopara (responsible for downy mildew) and Uncinula necator (responsible for powdery mildew). Similar results can be expected against the other microorganisms mentioned in this description.
  • the present invention makes it possible to significantly increase (more than 200%) and unexpected biological efficiency of industrial hydrogen peroxide (35%) by the use of various formulating agents, whose respective roles are still poorly defined to date, in the field of the fight against plant diseases such as vines, fruit trees, cereals, beets, potatoes, horticultural and flower crops.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The composition of the invention comprises hydrogen peroxide, at least one surface active agent, at least one peroxide stabilizing agent, at least one evaporation retarder, at least one adhesiveness enhancing agent and at least one anticorrosion agent or a sequestering agent, and provides, at the time of use, 10-20,000 ppm of hydrogen peroxide. The composition can also contain other conventional compatible fungicides. The invention also concerns a sporicide-fungicide made from said composition and a method of treating plants with said sporicide or said composition. The invention provides a formulation for combatting the spores and mycelium of numerous parasitic fungi more effectively than non-formulated hydrogen peroxide.

Description

Composition à base de peroxyde d'hydrogène formulé pour le traitement préventif et curatif des maladies foliaires et aériennes des végétaux. Composition based on hydrogen peroxide formulated for the preventive and curative treatment of leaf and air diseases of plants.
Le peroxyde d'hydrogène a reçu, depuis son identification en 1818 par Thénard, de nombreuses applications, principalement en chimie en raison de son pouvoir oxydant ou réducteur, selon le pH du milieu, ainsi que dans le domaine médical où il est utilisé per se ou en combinaison avec des alcools, d'autres agents antimicrobiens et des acides (voir par exemple le brevet US-A-4 900 721), et dans divers domaines industriels, tels que celui de la fabrication des textiles et de la pâte à papier où il est employé comme décolorant et agent de contrôle de la pollution, et celui de la métallurgie. Il a également été utilisé comme source d'énergie (comburant propulsif).Since its identification in 1818 by Thénard, hydrogen peroxide has received numerous applications, mainly in chemistry because of its oxidizing or reducing power, depending on the pH of the medium, as well as in the medical field where it is used per se. or in combination with alcohols, other antimicrobial agents and acids (see for example US-A-4,900,721), and in various industrial fields, such as the manufacture of textiles and pulp where it is used as a bleach and pollution control agent, and that of metallurgy. It has also been used as an energy source (propellant oxidizer).
Le peroxyde d'hydrogène a également été utilisé en agriculture, dans des applications relevant du rôle bactéricide qui lui est reconnu dans le domaine médical. Il a ainsi été étudié comme tel dans le traitement des graines ou des fruits après récolte, mais aussi en association avec d'autres composés dans la lutte contre les champignons parasites des plantes. Ainsi, le document JP-5 229 910 divulgue la combinaison du peroxyde d'hydrogène à un agent antimicrobien efficace contre Plasmodiophora brassicae, champignon responsable de la hernie du chou ; et le document US-A-5 079 868 divulgue la combinaison du peroxyde d'hydrogène avec de l'urée pour lutter notamment contre Peronospora et Phytophtora, deux champignons affectant la vigne. Le peroxyde d'hydrogène a également été utilisé seul pour ce type d'applications.Hydrogen peroxide has also been used in agriculture, in applications relating to the bactericidal role which is recognized in the medical field. It has thus been studied as such in the treatment of seeds or fruits after harvest, but also in combination with other compounds in the fight against parasitic fungi of plants. Thus, the document JP-5 229 910 discloses the combination of hydrogen peroxide with an antimicrobial agent effective against Plasmodiophora brassicae, the fungus responsible for the hernia of cabbage; and document US-A-5,079,868 discloses the combination of hydrogen peroxide with urea to fight in particular against Peronospora and Phytophtora, two fungi affecting the vine. Hydrogen peroxide has also been used alone for this type of application.
On notera que, du fait de sa présentation liquide et de sa solubilité dans l'eau, il n'est pas nécessaire de le formuler d'une manière particulière pour pouvoir le mettre en oeuvre. Ainsi, la demande de brevet européenne EP-A-0 347 731 divulgue un procédé de lutte contre les bactéries et parasites des plantes, et notamment le Botrytis, l'oidium et le mildiou de la vigne, qui consiste à pulvériser, après le début de l'infection, sur les parties aériennes des plantes, une solution renfermant de 0,05 à 5% en poids de peroxyde d'hydrogène à 35%, éventuellement associé à des composés supposés renforcer la lutte contre les parasites, tels que les composés du calcium, et/ou à des composés favorisant la croissance des plantes, tels que les composés du magnésium, et/ou à des peracides organiques et/ou à du soufre. L'inconvénient majeur de ce procédé connu est que les quantités de peroxyde d'hydrogène pulvérisées, sauf dans le cas particulier du botrytis de l'inflorescence, vont de 19,5 à 45 1/ha, les quantités préférées étant voisines de 19,5 à 30 1/ha, c'est-à-dire bien supérieures aux limites acceptables dans la pratique phytosanitaire, lesquelles doivent rester, au mieux, inférieures à 5 1/ha et, en tout cas, en dessous de 10 1/ha pour réduire autant que faire se peut les quantités de produit à transporter jusqu'au lieu du traitement.It will be noted that, because of its liquid presentation and its solubility in water, it is not necessary to formulate it in a particular manner in order to be able to use it. Thus, European patent application EP-A-0 347 731 discloses a process for combating plant bacteria and parasites, and in particular Botrytis, oidium and downy mildew, which consists of spraying, after the start of infection, on the aerial parts of plants, a solution containing 0.05 to 5% by weight of 35% hydrogen peroxide, possibly associated with compounds believed to enhance the fight against parasites, such as calcium compounds, and / or compounds promoting plant growth, such as magnesium compounds, and / or organic peracids and / or sulfur. The major drawback of this known process is that the quantities of sprayed hydrogen peroxide, except in the particular case of inflorescence botrytis, range from 19.5 to 45 l / ha, the preferred quantities being close to 19, 5 to 30 1 / ha, that is to say much higher than the limits acceptable in phytosanitary practice, which must remain, at best, less than 5 1 / ha and, in any case, below 10 1 / ha to reduce as much as possible the quantities of product to be transported to the place of treatment.
L'invention résoud ce problème en proposant une nouvelle formulation spécifique à base de peroxyde d'hydrogène qui permet de lutter efficacement contre les champignons pathogènes parasites des parties aériennes des végétaux, et en particulier de la vigne, un sporicide- fongicide de contact constitué par ladite formulation, ainsi qu'un procédé de lutte contre de tels champignons, qui consiste à pulvériser ladite formulation ou ledit sporicide- fongicide sur les plantes. Il a été découvert que la formulation particulière de l'invention a une efficacité telle que l'application d'une quantité de peroxyde d'hydrogène à l'hectare bien inférieure à celle pulvérisée selon l'art antérieur permet de détruire bien plus efficacement les champignons et les spores (5 1/ha de la formulation proposée, avec des valeurs extrêmes allant de 2 à 10 1/ha). Plus précisément, l'invention a pour objet :The invention solves this problem by proposing a new specific formulation based on hydrogen peroxide which makes it possible to fight effectively against pathogenic fungi parasites of the aerial parts of plants, and in particular of the vine, a contact sporicide-fungicide constituted by said formulation, as well as a method of combating such fungi, which consists in spraying said formulation or said sporicide-fungicide on plants. It has been discovered that the particular formulation of the invention has an effectiveness such that the application of a quantity of hydrogen peroxide per hectare much lower than that sprayed according to the prior art makes it possible to destroy the fungi and spores (5 1 / ha of the proposed formulation, with extreme values ranging from 2 to 10 1 / ha). More specifically, the subject of the invention is:
- d'une manière générale, une composition pour le traitement préventif et curatif des maladies foliaires et aériennes des végétaux, comprenant : a) du peroxyde d'hydrogène ; b) au moins un agent à activité de surface ; c) au moins un agent de stabilisation du peroxyde ; d) au moins un agent retardant l'évaporation ; e) au moins un agent améliorant l'adhésivité ; f) au moins un agent anti-corrosion, laquelle composition apporte, au moment de l'emploi, de 10 à 20.000 ppm de peroxyde d'hydrogène ; et- In general, a composition for the preventive and curative treatment of leaf and air diseases of plants, comprising: a) hydrogen peroxide; b) at least one surfactant; c) at least one peroxide stabilizing agent; d) at least one agent delaying evaporation; e) at least one tackifier; f) at least one anti-corrosion agent, which composition provides, at the time of use, from 10 to 20,000 ppm of hydrogen peroxide; and
- un sporicide-fongicide de contact constitué par ladite formulation. Comme agents à activité de surface, on peut utiliser : des alcools : des monalcools, tels que le méthanol, le propanol, le butanol ; l'éthylène-glycol ; des polyglycols, tels que le poly(éthylène-glycol), et leurs esters ; des poly-glycérols et leurs monoesters d'acides gras, le sorbitol ; des dérivés oxyéthyléniques et oxypropyléniques, tels que des mono- ou di-esters d'acides gras ; des éthers polyoxyéthyléniques et polyoxypropyléniques d'alcools gras ou d'acides-alcools ; des éthers de mercaptans ; des dérivés oxyéthyléniques et oxypropyléniques d'aminés ou d'amides d'aminoalcools ; des dérivés al ylarylpolyal ylèneoxyde ; des dérivés d'esters gras, tels que des dérivés des polyols esters de saccharose, de sorbitol ; et des éthers (poly)oxyéthyléniques et (poly)oxy¬ propyléniques des phénols, crésols, alkylphénols et alkylnaphtols.- a contact sporicide-fungicide constituted by said formulation. As surface active agents, there can be used: alcohols: monalcohols, such as methanol, propanol, butanol; ethylene glycol; polyglycols, such as poly (ethylene glycol), and their esters; poly-glycerols and their fatty acid monoesters, sorbitol; oxyethylenic and oxypropylenic derivatives, such as mono- or di-esters of fatty acids; polyoxyethylene and polyoxypropylene ethers of fatty alcohols or acid-alcohols; mercaptan ethers; oxyethylene and oxypropylene derivatives of amines or amides of amino alcohols; al ylarylpolyal yleneoxide derivatives; fatty ester derivatives, such as derivatives of the polyol esters of sucrose, of sorbitol; and (poly) oxyethylene and (poly) oxypropylene ethers of phenols, cresols, alkylphenols and alkylnaphthols.
Ces agents à activité de surface représentent d'environ 0,05 à environ 2% en poids de la formulation. Ils peuvent être utilisés seuls ou en combinaison. Ces composés sont disponibles auprès d'une diversité de fournisseurs, par exemple auprès de BASF sous les dénominations PLURONICR et TETRONICR, auprès de ICI sous la dénomination ATPLUSR, auprès de RHONE-POULENC sous les dénominations RHODAMINER, IGEPALR, ALKAMULR et ANTAR0XR, auprès de O NICHEM sous la dénomination TENSIOFIXR, auprès de UNION CARBIDE sous la dénomination TERGITOLR.These surface active agents represent from about 0.05 to about 2% by weight of the formulation. They can be used alone or in combination. These compounds are available from a variety of suppliers, for example from BASF under the names PLURONIC R and TETRONIC R , from ICI under the name ATPLUS R , from RHONE-POULENC under the names RHODAMINE R , IGEPAL R , ALKAMUL R and ANTAR0X R , with O NICHEM under the name TENSIOFIX R , with UNION CARBIDE under the name TERGITOL R.
La formulation renferme également d'environ 1 à environ 5% en poids d'au moins un agent de stabilisation du peroxyde, tel que de l'acide benzènesulfonique, de l'acide trifluoroacétique, de l'acide chlorhydrique, de l'acide nitrique, de l'acide phosphorique et de l'acide sulfurique, utilisés seuls ou en combinaison, qui sont couramment disponibles dans le commerce. La formulation renferme en outre de 0,05 à environ 1% d'au moins un agent anti-corrosion et/ou d'un ou plusieurs séquestrants, tels que le benzotriazole et/ou l'acide éthylène diamine tétraacétique (EDTA) .The formulation also contains from about 1 to about 5% by weight of at least one peroxide stabilizing agent, such as benzenesulfonic acid, trifluoroacetic acid, hydrochloric acid, nitric acid. , phosphoric acid and sulfuric acid, used alone or in combination, which are commonly available commercially. The formulation also contains from 0.05 to about 1% of at least one anti-corrosion agent and / or of one or more sequestrants, such as benzotriazole and / or ethylene diamine tetraacetic acid (EDTA).
Comme agents retardant l'évaporation, destinés à éviter que la formulation ne s'évapore une fois pulvérisée sur la plante et à réduire la vitesse de décomposition de la matière active appliquée à la plante, on peut utiliser d'environ 0,1 à environ 5% soit d'un ou plusieurs alcools, tels que du glycol ou de l'isopropanol, soit d'acide hexanedioïque, soit d'un mélange de ceux-ci.As evaporation delaying agents, intended to prevent the formulation from evaporating when sprayed on the plant and to reduce the rate of decomposition of the active ingredient applied to the plant, it is possible to use from about 0.1 to about 5% either of one or more alcohols, such as glycol or isopropanol, or of hexanedioic acid, or of a mixture of these.
Les agents améliorant l'adhésivité, ou réduisant le lessivage par la pluie, qui peuvent être utilisés dans la présente invention, comprennent d'environ 0,1 à environ 0,5% de dérivés de la pyrrolidone, tels que, par exemple, AGRIMAXR, AGRISYNTHR ou AGRIMERR, qui sont disponibles auprès de ISP.Tack improving agents or reducing rain leaching which can be used in the present invention include from about 0.1 to about 0.5% of pyrrolidone derivatives, such as, for example, AGRIMAX R , AGRISYNTH R or AGRIMER R , which are available from ISP.
La formulation selon l'invention peut également comprendre des composés qui n'ont pas d'influence sur l'efficacité de l'invention mais sont destinés à avertir le manipulateur, tels que des colorants εolubles dans l'eau (ACID RED, JAUNE SULFONE, etc..) et/ou des agents odorants (dénaturants olfactifs) présents jusqu'à environ 5% en poids dans la formulation (acide acétique, acide propionique, acide heptanoïque ou acide picrique, par exemple, utilisés seuls ou en combinaison).The formulation according to the invention can also comprise compounds which have no influence on the effectiveness of the invention but are intended to warn the manipulator, such as dyes soluble in water (ACID RED, YELLOW SULPHONE , etc.) and / or odorants (olfactory denaturants) present up to about 5% by weight in the formulation (acetic acid, propionic acid, heptanoic acid or picric acid, for example, used alone or in combination).
Selon une autre forme d'exécution de l'invention, la formulation renferme en outre un ou plusieurs fongicides compatibles choisis entre le soufre, les benzimidazoles, les dithiocarbamates, les dérivés du phénol, les phtali ides, les imides cycliques, les dérivés amines-amides, les dérivés diazines, les hétérocycles morpholines, imidazoles et triazoles. Dans ce cas, la formulation apporte, au moment de l'emploi, de 500 à 5.000 ppm de peroxyde d'hydrogène et une concentration classique, ou éventuellement réduite, dudit ou desdits fongicide(s) . On a noté que l'association du peroxyde d'hydrogène formulé avec un autre fongicide pourrait présenter un effet synergique.According to another embodiment of the invention, the formulation also contains one or more compatible fungicides chosen from sulfur, benzimidazoles, dithiocarbamates, phenol derivatives, phthaliides, cyclic imides, amine derivatives. amides, diazine derivatives, morpholine heterocycles, imidazoles and triazoles. In this case, the formulation provides, at the time of use, from 500 to 5,000 ppm of hydrogen peroxide and a conventional concentration, or possibly reduced, of said fungicide (s). It was noted that the combination of the formulated hydrogen peroxide with another fungicide could have a synergistic effect.
Trois exemples de formulations selon la présente invention sont donnés ci-dessous.Three examples of formulations according to the present invention are given below.
Formulation A peroxyde d'hydrogène 32,5% mouillant : éthylène diamine polyoxyéthylénique 1,0% stabilisant acide et anti¬ corrosion : mélange EDTA/H3P04 10/90 1,0% agents retardant l'évaporation et améliorant l'adhésivité : glycol/PVP 90/10 1,0% colorant JAUNE SULFONE 0,14% dénaturant olfactif acide acétique 0,5% eau qsp 100% Formulation B peroxyde d'hydrogène 32,5% mouillant : alkylphénoléthoxylate 0,5% stabilisant acide et anti¬ corrosion : mélange EDTA/acide nitrique 10/90 1,5% agents retardant l'évaporation et améliorant l'adhésivité : alcools/PVP 0,5% colorant : ACID RED 0,10% dénaturant olfactif : acide picrique 0,10% eau qsp 100%Formulation A hydrogen peroxide 32.5% wetting agent: ethylene diamine polyoxyethylene 1.0% acid stabilizer and anti¬ corrosion: EDTA / H 3 P0 4 10/90 mixture 1.0% agents delaying evaporation and improving adhesiveness : glycol / PVP 90/10 1.0% dye YELLOW SULFONE 0.14% odor denaturant acetic acid 0.5% water qs 100% Formulation B hydrogen peroxide 32.5% wetting agent: alkylphenolethoxylate 0.5% acid stabilizer and anti¬ corrosion: EDTA / nitric acid mixture 10/90 1.5% agents delaying evaporation and improving adhesiveness: alcohols / PVP 0.5% dye: ACID RED 0.10% odor denaturant: picric acid 0.10% water qs 100%
Formulation C peroxyde d'hydrogène à 35% 980 mlFormulation C 35% hydrogen peroxide 980 ml
TENSIOFIXR HS 5gTENSIOFIX R HS 5g
Ethylène glycol 50gEthylene glycol 50g
PVP 5gPVP 5g
^-6^10^4 2g H3PO4 10g^ -6 ^ 10 ^ 4 2g H3PO4 10g
CH3CH2COOH 3g colorant quelconque 0,7 à 1,4 g eau qsp 1 1CH 3 CH 2 COOH 3g any dye 0.7 to 1.4 g water qs 1 1
La formulation C, une fois diluée dans l'eau distillée pour ramener la concentration en peroxyde d'hydrogène à 32,5%, sera désignée par MRA dans la suite de la description. Il est bien entendu, toutefois, que les formulations selon l'invention peuvent être plus diluées, en fonction de l'objectif visé, et, en définitive, ces formulations peuvent contenir de 20 à 32,5% de peroxyde d'hydrogène, avec des variations corrélatives des agents de formulation. L'invention a également pour objet un procédé de traitement préventif ou curatif des maladies foliaires et aériennes des végétaux, qui consiste à pulvériser sur les végétaux de 50 à 400 1/ha, mais de préférence de 100 à 250 1/ha, du sporicide-fongicide ou de la formulation définis en termes généraux ci-dessus, ou encore un procédé qui consiste à soumettre lesdits végétaux conjointement à un traitement à l'aide de ladite formulation, laquelle apporte, au moment de l'emploi, entre 500 ppm et 5000 ppm de peroxyde d'hydrogène et est appliquée à raison de 50 à 400 1/ha, et à un traitement à l'aide d'un ou plusieurs fongicides choisis entre le soufre, les benzimidazoles, les dithiocarbamates, les dérivés du phénol, les phtali ides, les imides cycliques, les dérivés amines-amides, les dérivés diazines, les hétérocycles morpholines, imidazoles et triazoles et le phoséthyl-Al.Formulation C, once diluted in distilled water to reduce the hydrogen peroxide concentration to 32.5%, will be designated by MRA in the following description. It is understood, however, that the formulations according to the invention may be more diluted, depending on the objective sought, and, ultimately, these formulations may contain from 20 to 32.5% of hydrogen peroxide, with correlative variations of formulating agents. The subject of the invention is also a process for the preventive or curative treatment of leaf and air diseases of plants, which consists in spraying on plants 50 to 400 l / ha, but preferably 100 to 250 l / ha, of the sporicide -fungicide or of the formulation defined in general terms above, or else a process which consists in subjecting said plants jointly to a treatment using said formulation, which provides, at the time of use, between 500 ppm and 5000 ppm of hydrogen peroxide and is applied at a rate of 50 to 400 l / ha, and to a treatment using one or more fungicides chosen from sulfur, benzimidazoles, dithiocarbamates, phenol derivatives, phthalides, cyclic imides, amine-amide derivatives, diazine derivatives, morpholine heterocycles, imidazoles and triazoles and phosethyl-Al.
Il a été découvert que :It has been discovered that:
1") à des concentrations de moins de 500 ppm et parfois aussi faibles que 10 à 20 ppm, on observe la destruction totale des spores de ces organismes, lesquelles sont empêchées totalement et définitivement de germer. Il n'a pu être trouvé aucune spore qui n'ait été détruite par la formulation selon l'invention dans les essais de laboratoire.1 ") at concentrations of less than 500 ppm and sometimes as low as 10 to 20 ppm, the total destruction of the spores of these organisms is observed, which are completely and definitively prevented from germinating. No spore could be found which has not been destroyed by the formulation according to the invention in laboratory tests.
2e) à des concentrations comprises entre 5 000 à 20 000 ppm, la destruction des formes végétatives des champignons, dites formes "mycélium", est obtenue de manière plus ou moins rapide et totale : ces organismes sont bloqués dans leur développement, puis totalement détruits si le traitement est dupliqué. Ces deux types de résultats permettent de définir le peroxyde d'hydrogène comme un fongicide de contact, d'action rapide et de rémanence (persistance d'action) moyenne à faible.2 e ) at concentrations of between 5,000 and 20,000 ppm, the destruction of the vegetative forms of fungi, known as "mycelium" forms, is obtained more or less quickly and completely: these organisms are blocked in their development, then completely destroyed if the processing is duplicated. These two types of results make it possible to define hydrogen peroxide as a contact fungicide, rapid action and medium to low persistence (persistence of action).
3°) A des concentrations comprises entre 500 et 5 000 ppm, le peroxyde d'hydrogène joue le rôle d'un adjuvant actif aux programmes fongicides actuels. On peut émettre l'hypothèse que cette synergie résulte ,du fait que le peroxyde d'hydrogène, en détruisant facilement et totalement les spores à ces doses, ne laisse aux fongicides actuels, généralement spécialisés par maladie, que le soin d'effectuer la destruction du mycélium.3 °) At concentrations between 500 and 5000 ppm, hydrogen peroxide plays the role of an active adjuvant to current fungicide programs. We can send the hypothesis that this synergy results from the fact that hydrogen peroxide, by easily and totally destroying the spores at these doses, leaves to the current fungicides, generally specialized by disease, only the care of carrying out the destruction of the mycelium.
Il est bien entendu que les concentrations en peroxyde d'hydrogène indiquées ci-dessus correspondent à des fractions volumiques ou pondérales d'une formulation qui est ensuite appliquée dans 50 à 400 litres de bouillie par hectare. Par exemple, 20.000 ppm soit 2% de formulation dans 400 1/ha de bouillie correspondent à 8 1/ha de produit formulé pulvérisé.It is understood that the hydrogen peroxide concentrations indicated above correspond to volume or weight fractions of a formulation which is then applied in 50 to 400 liters of spray mixture per hectare. For example, 20,000 ppm or 2% of formulation in 400 l / ha of spray solution corresponds to 8 l / ha of sprayed formulated product.
Les maladies susceptibles d'un traitement sporicide- fongicide par la formulation selon l'invention sont celles où, à un stade ou à un autre, des spores et/ou des mycélium se sont développés en surface des organes aériens de la plante. Ces maladies peuvent être :The diseases susceptible to a sporicidal-fungicidal treatment by the formulation according to the invention are those where, at one stage or another, spores and / or mycelia have developed on the surface of the aerial organs of the plant. These diseases can be:
Oo ycètes : Pythium, Phytophtora, Plasmopara, Peronospora, Bremia et Albugo ;Oocetes: Pythium, Phytophtora, Plasmopara, Peronospora, Bremia and Albugo;
Basidiomycètes : Ustilago, Tilletia, Urocystis, Uro yces, Puccinia, Tranzchelia, Phragmidium, Gymnosporangium, Melampsora, Rhizoctonia, Stereu , Typhula, Phellinus ;Basidiomycetes: Ustilago, Tilletia, Urocystis, Uro yces, Puccinia, Tranzchelia, Phragmidium, Gymnosporangium, Melampsora, Rhizoctonia, Stereu, Typhula, Phellinus;
Ascomycetes ; Taphrina, Pénicillium, Aspergillus, Elsinoe, Erysiphe, Leveillula, Sphaerotheca, Microsphaera, Podospharea, Uncinula, Phyllactinia, Claviceps, Nectria, Gibberella, Guignardia, Mycosphaerella, Didymella, Ophiobolus, Venturia, Ceratocystis, Botrytis, Sclerotinia, Monilia, Pseudopeziza, Phacidiella, Coccomyces ;Ascomycetes; Taphrina, Penicillium, Aspergillus, Elsinoe, Erysiphe, Leveillula, Sphaerotheca, Microsphaera, Podospharea, Uncinula, Phyllactinia, Claviceps, Nectria, Gibberella, Guignardia, Mycosphaerella, Didymella, Ophiobolus Venturia, Ceratocystis, Botrytis, Sclerotinia, Monilia, Pseudopeziza, Phacidiella, Coccomyces;
Adelomycètes : Pho a, Phyllosticta, Aschochyta, Septoria, Fusicoccum, Coniothyrium, Gleosporium,Adelomycetes: Pho a, Phyllosticta, Aschochyta, Septoria, Fusicoccum, Coniothyrium, Gleosporium,
Colletotrichum, Kabathiella, Marssonina, Cylindrosporium,Colletotrichum, Kabathiella, Marssonina, Cylindrosporium,
Monilia, Botrytis, Ramularia, Oïdium, Thielaviopsis,Monilia, Botrytis, Ramularia, Powdery mildew, Thielaviopsis,
Fusicladium, Cladiosporium, Cylindrocarpon.Fusicladium, Cladiosporium, Cylindrocarpon.
La formulation selon l'invention peut être utilisée dans des pulvérisateurs convenables pour atteindre la partie malade de la plante : soit seule (si l'on approche de la récolte, par exemple, et que l'objectif recherché est l'efficacité avec absence de résidu sur la récolte), soit extemporanément en complément de fongicides organiques appropriés choisis parmi les familles suivantes . le soufreThe formulation according to the invention can be used in sprayers suitable for reaching the diseased part of the plant: either alone (if the harvest is approaching, for example, and the objective sought is efficiency with no residue on the crop), or extemporaneously in addition to appropriate organic fungicides chosen from the following families. sulfur
. les benzimidazoles, tel le carbendazime . les dithiocarbamates, tels le mancozebe et le thiurame . certains dérivés du phénol, tel le dinocap. benzimidazoles, such as carbendazim. dithiocarbamates, such as mancozebe and thiurame. certain phenol derivatives, such as dinocap
. les phtalimides, tels le phaltane et le captane . les imides cycliques, tel l'iprodione . les dérivés amines-amides, tels le cymoxanil, le métalaxyl, l'ofurace . les dérivés diazines, tel le nuarimol, . les hétérocycles morpholines (fenpropemorphe) imidazoles (prochloraze) triazoles (triadimephon),. phthalimides, such as phaltane and captan. cyclic imides, such as iprodione. amine-amide derivatives, such as cymoxanil, metalaxyl, ofurace. diazine derivatives, such as nuarimol,. morpholine heterocycles (fenpropemorph) imidazoles (prochloraze) triazoles (triadimephon),
. le phoséthyl-Al parmi d'autres ; soit en association (coformulation) avec la plupart des fongicides des familles citées ci-dessus, lorsque la compatibilité est bonne (cas du soufre notamment).. phosethyl-Al among others; either in combination (co-formulation) with most fungicides from the families mentioned above, when compatibility is good (sulfur in particular).
L'invention sera mieux comprise par référence aux exemples suivants qui sont donnés à titre d'illustration uniquement et n'ont pas pour but de limiter la portée de 1'invention. EXEMPLESThe invention will be better understood by reference to the following examples which are given by way of illustration only and are not intended to limit the scope of the invention. EXAMPLES
EXEMPLE 1- Essai in vitro sur Botrytis cinerea.EXAMPLE 1 In vitro test on Botrytis cinerea.
On a comparé l'efficacité in vitro de la formulationThe in vitro efficacy of the formulation was compared
MRA et d'une solution de peroxyde d'hydrogène du commerce àMRA and a commercial hydrogen peroxide solution at
35% qui a été diluée à l'aide d'eau distillée jusqu'à une concentration de 32,5% (ci-après MB), à l'encontre de35% which has been diluted with distilled water to a concentration of 32.5% (hereinafter MB), against
Botrytis cinerea. A cet effet, on a isolé une souche S9 de Botrytis cinerea sur une vigne et on l'a maintenue dans un milieu nutritif liquide CRISTOMAT-agar à 2% en boîtes de Pétri, à une température de 19°C et à l'obscurité.Botrytis cinerea. For this purpose, an S9 strain of Botrytis cinerea on a vine and kept in a 2% CRISTOMAT-agar liquid nutrient medium in Petri dishes, at a temperature of 19 ° C and in the dark.
L'essai a été effectué sur une plaque de culture cellulaire à 24 puits. On a introduit dans chaque puits 1,5 ml d'eau distillée additionnée soit de MB, soit de MRA, aux concentrations de 0 ; 0,002 ; 0,005 ; 0,01 et 0,02% en poids. On a ensuite ajouté 50 μl de suspension de conidies, à 105 spores/ml, dans chaque puits. La germination des conidies a été évaluée après 24 heures d'incubation à 19"C. Les résultats sont présentés dans le Tableau 1 où DE 50 et DE 95 représentent la dose efficace pour détruire respectivement 50% et 95% de la population des conidies.The assay was performed on a 24-well cell culture plate. 1.5 ml of distilled water was added to each well, supplemented with either MB or MRA, at concentrations of 0; 0.002; 0.005; 0.01 and 0.02% by weight. Then added 50 μl of conidia suspension, at 10 5 spores / ml, to each well. The germination of the conidia was evaluated after 24 hours of incubation at 19 ° C. The results are presented in Table 1 where DE 50 and DE 95 represent the effective dose for destroying 50% and 95% of the conidia population respectively.
Tableau 1Table 1
DE 50 DE 95FROM 50 FROM 95
MB 0,0068 μg/ml 0,0240 μg/ml MRA 0,0028 μg/ml 0,0089 μg/mlMB 0.0068 μg / ml 0.0240 μg / ml MRA 0.0028 μg / ml 0.0089 μg / ml
Il ressort du Tableau 1 ci-dessus que la formulation MRA est 2,5 à 3 fois plus efficace que le peroxyde d'hydrogène pris séparément. D'autres essais in vitro, réalisés dans des conditions similaires à celles de l'Exemple 1, qui rendent compte de l'activité préventive de la formulation selon l'invention, ont montré que la formulation MRA diluée à 2% permettait de tuer les spores et les mycélium d'Erysiphe graminis (en curatif 48 heures) et diluée à 0,002% les spores de Septoria nodorum et tritici (en préventif). EXEMPLE 2- Essai in vitro sur Monilia fructigena.It appears from Table 1 above that the MRA formulation is 2.5 to 3 times more effective than the hydrogen peroxide taken separately. Other in vitro tests, carried out under conditions similar to those of Example 1, which account for the preventive activity of the formulation according to the invention, have shown that the MRA formulation diluted to 2% made it possible to kill the spores and mycelium of Erysiphe graminis (curative 48 hours) and diluted to 0.002% the spores of Septoria nodorum and tritici (preventive). EXAMPLE 2- In vitro test on Monilia fructigena.
On a comparé l'efficacité in vitro des deux produits MB et MRA ci-dessus à l'encontre de deux souches de Monilia fructigena (isolats 1519 et 1097 de Monilia fructigena isolés sur pomme). Les souches ont été maintenues en incubation sur un milieu nutritif DIAMALT-Agar à 2%, à une température de 19°C et à l'obscurité.The in vitro efficacy of the two products MB and MRA above was compared against two strains of Monilia fructigena (isolates 1519 and 1097 of Monilia fructigena isolated on apple). The strains were kept in incubation on a 2% DIAMALT-Agar nutrient medium, at a temperature of 19 ° C and in the dark.
Plus précisément, le produit MB et la formulation MRA ont été utilisés à des concentrations de 0,002 ; 0,02 ; 0,2 et 2%.More specifically, the product MB and the formulation MRA were used at concentrations of 0.002; 0.02; 0.2 and 2%.
Chaque boîte de Pétri contenant 20 ml de DIAMALT-Agar a été ensemencée en son centre par un implant mycélien en pleine croissance, de 4 mm de diamètre.Each Petri dish containing 20 ml of DIAMALT-Agar was seeded in the center with a growing mycelial implant, 4 mm in diameter.
Après ensemencement, on a mesuré les diamètres des plages mycéliennes et on en a déduit la dose efficace pour détruire 50% des champignons (DE 50) et la dose efficace pour détruire 95% des champignons (DE 95).After sowing, the diameters of the mycelial areas were measured and the effective dose for destroying 50% of the fungi (ED 50) and the effective dose for destroying 95% of the fungi (DE 95) were deduced therefrom.
Les résultats sont présentés dans le Tableau 2 ci- dessous :The results are presented in Table 2 below:
Tableau 2Table 2
MRA MB DE 50 DE 95 DE 50 DE 95 1519 0,12 μg/ml 5,05 μg/ml 0,2 μg/ml 11,2 μg/ml 1097 0,07 μg/ml 3,48 μg/ml 0,11 μg/ml 5,35 μg/mlMRA MB DE 50 DE 95 DE 50 DE 95 1519 0.12 μg / ml 5.05 μg / ml 0.2 μg / ml 11.2 μg / ml 1097 0.07 μg / ml 3.48 μg / ml 0, 11 μg / ml 5.35 μg / ml
Bien que l'isolât 1519 paraisse moins sensible que l'isolât 1097 vis-à-vis des deux préparations, on déduit de ces résultats que la formulation MRA est approximativement 1,8 à 2 fois plus active que le produit MB (concentration en peroxyde environ 1,8 à 2 fois plus faible pour le même résultat) .Although isolate 1519 appears less sensitive than isolate 1097 to the two preparations, it is deduced from these results that the MRA formulation is approximately 1.8 to 2 times more active than the product MB (peroxide concentration about 1.8 to 2 times lower for the same result).
Ces résultats confirment la supériorité de la formulation MRA par rapport au peroxyde d'hydrogène non formulé, déjà mise en évidence à l'exemple 1. EXEMPLE 3- Essai en champ sur Botrytis.These results confirm the superiority of the MRA formulation compared to the unformulated hydrogen peroxide, already demonstrated in Example 1. EXAMPLE 3 Field test on Botrytis.
Fin 1993, des pulvérisations expérimentales ont été effectuées, sur de la vigne, en Champagne, en utilisant la formulation MRA à la concentration de 0,5 %, 1 % et 2 %. On a observé, 24 heures plus tard, un nettoyage partiel du Botrytis à 0,5 % et 1 %, et un nettoyage total à 2 %. La zone traitée à 2 % ne montre aucune reprise sensible du champignon, cinq jours après le premier contrôle. Les irrégularités observées dans les efficacités relevées à 0,5 % et 1 % sont partiellement imputables à la qualité imparfaite de la pulvérisation.At the end of 1993, experimental sprays were carried out on vines in Champagne, using the MRA formulation at a concentration of 0.5%, 1% and 2%. 24 hours later, partial cleaning was observed Botrytis at 0.5% and 1%, and a total cleaning at 2%. The zone treated at 2% shows no significant recovery of the fungus, five days after the first control. The irregularities observed in the efficiencies noted at 0.5% and 1% are partially attributable to the imperfect quality of the spraying.
EXEMPLE 4- Essai en champ sur Botrytis : comparaison avec un témoin non traité.EXAMPLE 4 Field test on Botrytis: comparison with an untreated control.
En Languedoc, à Ledenon, une vigne de Carignan très affectée par un orage violent (qui constitue une condition très favorable au développement du Botrytis) a été traitée en pulvérisant 200 1/ha d'une "bouillie" constituée de MRA diluée à 2%, ce qui correspond à une dose de 41/ha de MRA. Une forte pluie de 26 mm est survenue 5 jours plus tard et la récolte a été effectuée 5 jours après. On a comparé un témoin non traité (en abrégé TNT) à la formulation MRA. Les résultats sont donnés dans le Tableau 3.In Languedoc, in Ledenon, a Carignan vine very affected by a violent storm (which constitutes a very favorable condition for the development of Botrytis) was treated by spraying 200 1 / ha of a "porridge" made up of MRA diluted to 2% , which corresponds to a dose of 41 / ha of MRA. Heavy rain of 26 mm occurred 5 days later and the harvest was carried out 5 days later. An untreated control (abbreviated as TNT) was compared to the MRA formulation. The results are given in Table 3.
Tableau 3Table 3
Avant traitement A la récolteBefore treatment At harvest
TNT MRATNT MRA
% grappes saines 33% 4,5% 20%% healthy clusters 33% 4.5% 20%
% moyen d'attaque par grappe* 14% 56% 22%% average attack per cluster * 14% 56% 22%
* évalué visuellement* visually assessed
On notera que la cinétique d'évolution du botrytis sur le témoin non traité est de 4 fois (56/14 = 4), contre 1,5 fois (22/14 = 1,5) sur la vigne traitée avec la formulation selon l'invention. De plus, on obtient 8,3 tonnes de récolte saine pour la modalité traitée à l'aide de MRA contre 4,3 tonnes de récolte saine pour le témoin non traité, soit une récolte saine presque doublée. EXEMPLE 5- Essai en champ sur Botrytis : comparaison avec la vinchlozoline.It will be noted that the kinetics of evolution of the botrytis on the untreated control is 4 times (56/14 = 4), against 1.5 times (22/14 = 1.5) on the vine treated with the formulation according to l 'invention. In addition, we obtain 8.3 tonnes of healthy harvest for the modality treated using MRA against 4.3 tonnes of healthy harvest for the untreated control, a healthy harvest almost doubled. EXAMPLE 5 Field trial on Botrytis: comparison with vinchlozoline.
Dans cet exemple, on a réalisé un essai comparatif entre la formulation MRA et une préparation de vinchlozoline (utilisée comme traitement de référence), appliquées sur le cépage Pinot noir, en Champagne, dans l'Aube. On a effectué quatre répétitions (sur quatre parcelles différentes) d'un même essai, qui consistait à pulvériser 400 1/ha de la formulation MRA diluée jusqu'à 2% (soit 8 1/ha de MRA), aux stades phénologiques classiques D (3 semaines avant récolte) et D + 8 (8 jours plus tard).In this example, a comparative test was carried out between the MRA formulation and a vinchlozoline preparation (used as a reference treatment), applied to the Pinot noir grape variety, in Champagne, in Aube. Four repetitions were carried out (on four different plots) of the same test, which consisted of spraying 400 1 / ha of the MRA formulation diluted up to 2% (ie 8 1 / ha of MRA), at the classic phenological stages D (3 weeks before harvest) and D + 8 (8 days later).
Sur la modalité de référence, on a effectué quatre traitements avec la vinchlozoline, aux stades phénologiques A (floraison), B (fermeture de la grappe), C (véraison) et D de la vigne, à raison de 750 g de matière active par hectare, soit 1,5 kg/ha de RONILANR fourni par BASF, ce qui correspond à la dose homologuée.On the reference modality, four treatments were carried out with vinchlozoline, at the phenological stages A (flowering), B (closure of the cluster), C (veraison) and D of the vine, at the rate of 750 g of active ingredient per hectare, i.e. 1.5 kg / ha of RONILAN R supplied by BASF, which corresponds to the approved dose.
Un témoin non traité (TNT) a également été évalué. Les résultats relevés au moment de la récolte sont donnés dans le Tableau 4.An untreated control (TNT) was also evaluated. The results recorded at the time of harvest are given in Table 4.
Tableau 4Table 4
vinchlozoline MRA TNTvinchlozoline MRA TNT
%moyen de grappes saines 21% 29% 6%Average% of healthy clusters 21% 29% 6%
%moyen d'attaque par grappe 28% 17% 27% rendement de ven¬ dange saine 7650 kg/ha 10100 kg/ha 6200 kg/ha degré d'alcool dans la grappe pressée 8,15 8,13 8,2% average attack per bunch 28% 17% 27% yield of healthy ven¬ 7670 kg / ha 10,100 kg / ha 6,200 kg / ha degree of alcohol in the pressed bunch 8.15 8.13 8.2
En conclusion, deux traitements à 8 jours d'intervalle peu avant la récolte, en utilisant la formulation MRA, donnent des résultats bien supérieurs à ceux obtenus avec quatre traitements à l'aide de la référence vinchlozoline. appliqués en cours de saison. La différence de quantité récoltée est économiquement très importante (+ 2.500 kg). EXEMPLE 6 - Essai sur l'oïdium de la vigne.In conclusion, two treatments 8 days apart shortly before harvest, using the MRA formulation, give results far superior to those obtained with four treatments using the vinchlozoline reference. applied during the season. The difference in the quantity harvested is economically very significant (+ 2,500 kg). EXAMPLE 6 - Test on powdery mildew of the vine.
On a réalisé un essai comparatif entre la formulation MRA et du soufre mouillable (c'est-à-dire une ' poudre pulvérisable constituée de soufre additionné de mouillant) dans le Roussillon, à Sainte-Colombe, sur un cépage Syrah. A cet effet, quatre répétitions ont été effectuées en pulvérisant environ 230 1/ha de "bouillie" de MRA diluée jusqu'à 2%, appliquée en six traitements espacés d'environ 14 jours les uns des autres (dose/ha de MRA = 4,6 litres).A comparative test was carried out between the MRA formulation and wettable sulfur (that is to say a ' sprayable powder consisting of sulfur with wetting agent) in Roussillon, at Sainte-Colombe, on a Syrah grape. For this purpose, four repetitions were carried out by spraying approximately 230 1 / ha of "slurry" of MRA diluted up to 2%, applied in six treatments spaced approximately 14 days apart from each other (dose / ha of MRA = 4.6 liters).
On a testé en parallèle du soufre mouillable THIOVIT, fourni par SANDOZ, à raison également de 6 pulvérisations de 12,5 kg/ha. Un témoin non traité (TNT) a également été évalué.Wettable sulfur THIOVIT, supplied by SANDOZ, was tested in parallel, also at the rate of 6 sprays of 12.5 kg / ha. An untreated control (TNT) was also evaluated.
Les résultats sont rassemblés dans le Tableau 5.The results are collated in Table 5.
Tableau 5Table 5
THIOVIT MRA TNTTHIOVIT MRA TNT
% moyen d'attaque par grappe 1,13% 1,05% 16%% average attack per cluster 1.13% 1.05% 16%
Les deux produits ne présentent pas de différence significative. Cet exemple démontre qu'un produit assez peu rémanent, comme le peroxyde d'hydrogène convenablement formulé, peut avantageusement être comparé au soufre, produit classique de la lutte contre l'oïdium. C'est à son mode d'action à la fois préventif et curatif que la formulation MRA doit d'avoir eu une telle efficacité. Compte-tenu de son activité déjà démontrée vis-à-vis du Botrytis, on peut en déduire que la formulation de • MRA offre une certaine polyvalence intéressante sur le plan économique. EXEMPLE 7- Essai sur le mildiou de la vigne comparaison avec l'association cymoxanil + mancozebe.There is no significant difference between the two products. This example demonstrates that a relatively non-persistent product, such as suitably formulated hydrogen peroxide, can advantageously be compared to sulfur, a conventional product for combating powdery mildew. It is to its mode of action, both preventive and curative, that the MRA formulation must have had such effectiveness. Given its already demonstrated activity with respect to Botrytis, it can be deduced that the formulation of • MRA offers a certain interesting versatility on the economic level. EXAMPLE 7 Test on downy mildew of the vine compared with the association cymoxanil + mancozebe.
Un essai a été effectué en Languedoc, sur six parcelles différentes, qui ont été chacune soumises à 11 traitements espacés de 10 jours les uns des autres. La formulation MRA diluée jusqu'à 2%, a été appliquée à ces vignes par pulvérisation de quantités progressives de bouillie allant de 140 à 200 1/ha.A trial was carried out in Languedoc, on six different plots, which were each subjected to 11 treatments spaced 10 days apart. The MRA formulation, diluted up to 2%, was applied to these vines by spraying progressive amounts of spray ranging from 140 to 200 l / ha.
La formulation selon l'invention a été comparée à l'association cymoxanil + mancozebe, qui est la référenceThe formulation according to the invention was compared with the combination cymoxanil + mancozebe, which is the reference
Protection des Végétaux (REMILTINE PEPITER, fournie parPlant Protection (REMILTINE PEPITE R , supplied by
SANDOZ), appliquée à la dose homologuée de 3 kg/ha (0,1 +SANDOZ), applied at the approved rate of 3 kg / ha (0.1 +
1,395 kg de matière active).1.395 kg of active ingredient).
Un témoin non traité (TNT) a par ailleurs été évalué. L'essai, conduit sous contamination artificielle et brumisation, démontre une attaque moyenne, mais un contrôle de la maladie tout à fait comparable pour les deux modalités et ce, statistiquement.An untreated control (TNT) was also evaluated. The test, conducted under artificial contamination and misting, shows a moderate attack, but a control of the disease quite comparable for the two methods and this, statistically.
Les résultats sont résumés dans le Tableau 6 ci- dessous.The results are summarized in Table 6 below.
Tableau 6Table 6
%moyen d'attaque %moyen d'attaque sur feuille sur grappe à la véraison% average attack% average attack on leaf on cluster at veraison
TNT 28,85% (a) 8 , 78% ( a )TNT 28.85% (a) 8, 78% (a)
REMILTINE PEPITE1 0,43% (b) 0 , 05% (b )REMILTINE PEPITE 1 0.43% (b) 0.05% (b)
MRA 0,36% (b) 0 , 08% (b )MRA 0.36% (b) 0.08% (b)
Classement Très hautement Très hautement statistique significatif significatifRanking Very highly Very highly significant statistically significant
La différence entre (a) et (b) est significative, contrairement à la différence entre les résultats notés (b) . EXEMPLE 8- Essai sur la pourriture grise : effet synergique de l'association MRA/vinchlozoline.The difference between (a) and (b) is significant, unlike the difference between the results noted (b). EXAMPLE 8 - Gray mold test: synergistic effect of the MRA / vinchlozoline combination.
On a comparé, en Val de Loire, en zone résistante, l'efficacité de la vinchlozoline employée seule et employée avec la formulation MRA jouant ici le rôle d'un adjuvant au fongicide de base. Les résultats obtenus sont les suivants :We compared, in the Loire Valley, in the resistant zone, the efficacy of vinchlozoline used alone and used with the MRA formulation playing here the role of an adjuvant to the basic fungicide. The results obtained are as follows:
vinchlozolinevinchlozoline
750 g de matière active/ha 35 % d'efficacité750 g of active ingredient / ha 35% efficiency
vi + 67 % d'efficacité fo
Figure imgf000018_0001
vi + 67% efficiency fo
Figure imgf000018_0001
Malgré la baisse d'efficacité due aux phénomènes de résistance présents dans de nombreux vignobles d'Europe occidentale, le contrôle de la maladie par la vinchlozoline peut être presque doublé par l'apport de l'adjuvant à base de peroxyde d'hydrogène.Despite the decrease in efficacy due to resistance phenomena present in many vineyards in Western Europe, the control of the disease by vinchlozoline can be almost doubled by the addition of the adjuvant based on hydrogen peroxide.
Les exemples ci-dessus et la description précédente démontrent que des concentrations de 2% de la formulation selon l'invention donnent de très bons résultats, aussi bien au laboratoire, dans des essais in vitro sur :The above examples and the preceding description demonstrate that concentrations of 2% of the formulation according to the invention give very good results, both in the laboratory, in in vitro tests on:
Monilia (responsable de la moniliose), Botrytis (responsable du botrytis ou pourriture), Erysiphe (responsable de l'oïdium des céréales) et Septoria nodorum (responsable de la septoriose des céréales), qu'au vignoble, dans des essais sur : Botrytis, Plasmopara (responsable du mildiou) et Uncinula necator (responsable de l'oïdium). On peut s'attendre à obtenir des résultats analogues à l'encontre des autres micro-organismes mentionnés dans la présente description.Monilia (responsible for moniliosis), Botrytis (responsible for botrytis or rot), Erysiphe (responsible for powdery mildew in cereals) and Septoria nodorum (responsible for septoria blight in cereals), only in the vineyard, in tests on: Botrytis , Plasmopara (responsible for downy mildew) and Uncinula necator (responsible for powdery mildew). Similar results can be expected against the other microorganisms mentioned in this description.
D'une manière générale, il a été démontré que la présente invention permet d'augmenter de façon significative (plus de 200%) et inattendue l'efficacité biologique du peroxyde d'hydrogène industriel (à 35%) par la mise en oeuvre de divers agents de formulation, dont les rôles respectifs sont encore mal définis à ce jour, dans le domaine de la lutte contre les maladies des plantes telles que la vigne, les arbres fruitiers, les céréales, les betteraves, les pommes de terre, les cultures horticoles et florales.In general, it has been demonstrated that the present invention makes it possible to significantly increase (more than 200%) and unexpected biological efficiency of industrial hydrogen peroxide (35%) by the use of various formulating agents, whose respective roles are still poorly defined to date, in the field of the fight against plant diseases such as vines, fruit trees, cereals, beets, potatoes, horticultural and flower crops.
On notera que, bien que dans la description qui précède on se soit référé à une application du sporicide ou des compositions selon l'invention par pulvérisation, d'autres techniques sont utilisables telles que le badigeon et l'inclusion dans les eaux d'aspersion. It will be noted that, although in the foregoing description, reference has been made to an application of the sporicide or of the compositions according to the invention by spraying, other techniques can be used such as whitewash and inclusion in spray water. .

Claims

REVENDICATIONS
1- Composition pour le traitement préventif et curatif des maladies foliaires et aériennes des végétaux, comprenant : a) du peroxyde d'hydrogène ; b) au moins un agent à activité de surface ; c) au moins un agent de stabilisation du peroxyde ; d) au moins un agent retardant l'évaporation ; e) au moins un agent améliorant l'adhésivité ; f) au moins un agent anti-corrosion et/ou un séquestrant, laquelle composition apporte, au moment de l'emploi, de 10 à 20.000 ppm de peroxyde d'hydrogène.1- Composition for the preventive and curative treatment of leaf and air diseases of plants, comprising: a) hydrogen peroxide; b) at least one surfactant; c) at least one peroxide stabilizing agent; d) at least one agent delaying evaporation; e) at least one tackifier; f) at least one anti-corrosion agent and / or a sequestering agent, which composition provides, at the time of use, from 10 to 20,000 ppm of hydrogen peroxide.
2- Composition selon la revendication 1, caractérisée en ce qu'elle renferme d'environ 20 à environ 32,5% en poids de peroxyde d'hydrogène.2- Composition according to claim 1, characterized in that it contains from about 20 to about 32.5% by weight of hydrogen peroxide.
3- Composition selon la revendication 1 ou 2, caractérisée en ce qu'elle renferme d'environ 0,05 à environ 2% en poids d'agent à activité de surface. 4- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle renferme d'environ 1 à environ 5% en poids d'agent de stabilisation.3- Composition according to claim 1 or 2, characterized in that it contains from about 0.05 to about 2% by weight of surface activity agent. 4- Composition according to any one of the preceding claims, characterized in that it contains from about 1 to about 5% by weight of stabilizing agent.
5- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle renferme de 0,05 à environ 1% en poids d'agent anti-corrosion et/ou de séquestrant.5- Composition according to any one of the preceding claims, characterized in that it contains from 0.05 to about 1% by weight of anti-corrosion agent and / or of sequestering agent.
6- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle renferme d'environ 0,1 à environ 5% en poids d'agent retardant l'évaporation.6- Composition according to any one of the preceding claims, characterized in that it contains from about 0.1 to about 5% by weight of agent delaying evaporation.
7- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle renferme d'environ 0,1 à environ 0,5% en poids d'agent améliorant l'adhésivité. 8- Composition selon l'une .quelconque des revendications précédentes, caractérisé en ce que l'agent à activité de surface est choisi dans le groupe consistant en : les monalcools ; l'éthylène-glycol ; les polyglycols et leurs esters ; les polyglycérols et leurs monoesters d'acides gras, le sorbitol ; les dérivés oxyéthyléniques et oxypropyléniques ; les éthers polyoxyéthyléniques et polyoxypropyléniques d'alcools gras ou d'acides-alcools ; les éthers de mercaptans ; les dérivés oxyéthyléniques et oxypropyléniques d'aminés ou d'amides d'aminoalcools ; les dérivés alkylarylpolyalkylèneoxyde ; les dérivés d'esters gras ; et les éthers (poly)oxyéthyléniques et (poly)oxypropyléniques des phénols, crésols, alkylphénols et alkylnaphtols. 9- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent de stabilisation du peroxyde est choisi dans le groupe consistant en : l'acide benzènesulfonique, l'acide trifluoroacétique, l'acide chlorhydrique, l'acide nitrique, l'acide phosphorique et l'acide sulfurique.7- Composition according to any one of the preceding claims, characterized in that it contains from about 0.1 to about 0.5% by weight of agent improving adhesiveness. 8- Composition according to one. Some of the preceding claims, characterized in that the surface activity agent is chosen from the group consisting of: monalcohols; ethylene glycol; polyglycols and their esters; polyglycerols and their fatty acid monoesters, sorbitol; oxyethylene and oxypropylene derivatives; polyoxyethylenic and polyoxypropylene ethers of fatty alcohols or acid-alcohols; mercaptan ethers; oxyethylene and oxypropylene derivatives of amines or amides of amino alcohols; alkylarylpolyalkyleneoxide derivatives; fatty ester derivatives; and the (poly) oxyethylene and (poly) oxypropylene ethers of phenols, cresols, alkylphenols and alkylnaphthols. 9- Composition according to any one of the preceding claims, characterized in that the peroxide stabilizing agent is chosen from the group consisting of: benzenesulfonic acid, trifluoroacetic acid, hydrochloric acid, nitric acid , phosphoric acid and sulfuric acid.
10- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent retardant l'évaporation est choisi dans le groupe consistant en : les alcools, tels que l'isopropanol ou le glycol, et l'acide hexanedioïque.10- Composition according to any one of the preceding claims, characterized in that the agent delaying evaporation is chosen from the group consisting of: alcohols, such as isopropanol or glycol, and hexanedioic acid.
11- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent améliorant l'adhésivité est choisi parmi les dérivés de la pyrrolidone. 12- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que l'agent anti-corrosion est le benzotriazole.11- Composition according to any one of the preceding claims, characterized in that the tackifier improving agent is chosen from pyrrolidone derivatives. 12- Composition according to any one of the preceding claims, characterized in that the anti-corrosion agent is benzotriazole.
13- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le séquestrant est l'acide éthylène diamine tétraacétique (EDTA) . 14- Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle renferme en outre un ou plusieurs fongicides compatibles choisis entre le soufre, les benzimidazoles, les dithiocarbamates, les dérivés du phénol, les phtalimides, les imides cycliques, les dérivés amines-amides, les dérivés diazines, les hétérocycles morpholines, imidazoles et triazoles, et en ce qu'elle apporte, au moment de l'emploi, de 500 à 5.000 ppm de peroxyde d'hydrogène et une concentration classique ou réduite dudit ou desdits fongicide(s) .13- Composition according to any one of the preceding claims, characterized in that the sequestrant is ethylene diamine tetraacetic acid (EDTA). 14- Composition according to any one of the preceding claims, characterized in that it also contains one or more compatible fungicides chosen from sulfur, benzimidazoles, dithiocarbamates, phenol derivatives, phthalimides, cyclic imides, amine-amide derivatives, diazine derivatives, morpholine heterocycles, imidazoles and triazoles, and in that it provides, at the time of use, from 500 to 5,000 ppm of hydrogen peroxide and a conventional or reduced concentration of said or said fungicide (s).
15- Sporicide-fongicide de contact constitué par la formulation selon l'une quelconque des revendications précédentes. 16- Procédé de traitement préventif ou curatif des maladies foliaires et aériennes des végétaux, caractérisé en ce qu'il consiste à pulvériser sur les végétaux de 50 à 400 1/ha, de préférence de 100 à 250 1/ha, de la formulation selon l'une quelconque des revendications 1 à 14 ou du sporicide selon la revendication 15.15- Contact sporicide-fungicide constituted by the formulation according to any one of the preceding claims. 16- A method of preventive or curative treatment of leaf and air diseases of plants, characterized in that it consists in spraying on plants from 50 to 400 1 / ha, preferably from 100 to 250 1 / ha, of the formulation according to any one of claims 1 to 14 or the sporicide according to claim 15.
17- Procédé de traitement préventif ou curatif des maladies foliaires et aériennes des végétaux, caractérisé en ce qu'il consiste à soumettre lesdits végétaux conjointement à un traitement à l'aide de la formulation selon l'une quelconque des revendications 1 à 13, laquelle formulation apporte, au moment de l'emploi, entre 500 et 5.000 ppm de peroxyde d'hydrogène et est appliquée, à raison de 50 à 400 1/ha, et à un traitement à l'aide d'un ou plusieurs fongicides choisis entre le soufre, les benzimidazoles, les dithiocarbamates, les dérivés du phénol, les phtalimides, les imides cycliques, les dérivés amines-amides, les dérivés diazines, les hétérocycles morpholines, imidazoles et triazoles et le phoséthyl-Al. 17- A method of preventive or curative treatment of leaf and air diseases of plants, characterized in that it consists in subjecting said plants jointly to a treatment using the formulation according to any one of claims 1 to 13, which formulation provides, at the time of use, between 500 and 5,000 ppm of hydrogen peroxide and is applied, at a rate of 50 to 400 1 / ha, and to a treatment using one or more fungicides chosen from sulfur, benzimidazoles, dithiocarbamates, phenol derivatives, phthalimides, cyclic imides, amine-amide derivatives, diazine derivatives, morpholine heterocycles, imidazoles and triazoles and phosethyl-Al.
PCT/FR1995/000516 1994-04-22 1995-04-20 Hydrogen peroxide composition formulated for the preventive and curative treatment of diseases affecting the foliage and aerial parts of plants WO1995028840A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9404860A FR2718924B1 (en) 1994-04-22 1994-04-22 Application of hydrogen peroxide for the preventive and curative treatment of leaf and air diseases of plants.
FR94/04860 1994-04-22

Publications (1)

Publication Number Publication Date
WO1995028840A1 true WO1995028840A1 (en) 1995-11-02

Family

ID=9462416

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR1995/000516 WO1995028840A1 (en) 1994-04-22 1995-04-20 Hydrogen peroxide composition formulated for the preventive and curative treatment of diseases affecting the foliage and aerial parts of plants

Country Status (2)

Country Link
FR (1) FR2718924B1 (en)
WO (1) WO1995028840A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6024986A (en) * 1999-05-24 2000-02-15 Ecolab Inc. Method of protecting growing plants from the effects of plant pathogens
WO2013096814A1 (en) * 2011-12-22 2013-06-27 Bui Huyen Phuong Non-corrosive stable peracetic acid concentrate solution
WO2020025816A1 (en) * 2018-08-03 2020-02-06 Compagnie Pour Le Haut Commerce Citrate perhydrates and uses thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0712905D0 (en) * 2007-07-04 2007-08-15 Reckitt Benckiser Uk Ltd Hard surface treatment compositions with improved mold or fungi remediation properties

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR401898A (en) * 1908-08-12 1909-09-18 Marie Adrien Eybert Process for the treatment of fungal and microbial diseases of plants
FR2090369A1 (en) * 1970-05-29 1972-01-14 Henkel & Cie Gmbh
JPS53113025A (en) * 1977-02-16 1978-10-03 Mitsubishi Gas Chem Co Inc Proliferation inhibitor for microorganisms
US4518585A (en) * 1978-05-01 1985-05-21 Sterling Drug Inc. Hydrogen peroxide disinfecting and sterilizing compositions
JPS6142600A (en) * 1984-08-06 1986-03-01 花王株式会社 Fungicidal composition
JPS61158907A (en) * 1985-01-07 1986-07-18 Kao Corp Mildew-removing agent composition
EP0252278A2 (en) * 1986-06-09 1988-01-13 Henkel Kommanditgesellschaft auf Aktien Disinfecting agents and their use in disinfecting the skin and mucous membranes
EP0347731A2 (en) * 1988-06-18 1989-12-27 Helmut Schätzlein Process for controlling plant pests, particularly on vines, hop stems or the like
JPH02115104A (en) * 1988-10-21 1990-04-27 Sakae Funamizu Sterilizing and controlling agent against blight of tree and using thereof
US5079868A (en) * 1990-06-25 1992-01-14 Union Oil Company Of California Plant treatment with urea peroxide
WO1992007465A1 (en) * 1988-05-02 1992-05-14 Lester Technologies Corporation Microbiocidal combinations of materials and their use
US5130124A (en) * 1991-05-01 1992-07-14 Isp Investments Inc. Stabilized, aqueous, film-forming antimicrobial compositions of hydrogen peroxide
EP0524150A1 (en) * 1991-07-19 1993-01-20 Ciba-Geigy Ag Improvement in hydrogen peroxide disinfection solutions
JPH05213686A (en) * 1992-01-31 1993-08-24 Gold Kosan Kk Plant physiological activity accelerator for greenhouse culture
JPH06121619A (en) * 1992-10-12 1994-05-06 Gold Kosan Kk Method for agrichemical-free culture

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55167207A (en) * 1979-06-18 1980-12-26 Nippon Peroxide Co Ltd Prevention and remedy for "murenae" disease
DD239109A1 (en) * 1985-07-08 1986-09-17 Veg Gartenbau MEANS FOR DETERMINING SEWAGE SOLUTIONS AND WATER IN GARDENING
FR2663852A1 (en) * 1990-07-02 1992-01-03 Ferlot Paul The invention relates to the manufacture of antiseptics and disinfectants. It is characterised by a mixing of powdered alkyldimethylbenzylammonium chlorides, iodides or bromides and powdered hydrogen peroxide
JPH05229910A (en) * 1992-02-07 1993-09-07 Hodogaya Chem Co Ltd Root knot controlling method

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR401898A (en) * 1908-08-12 1909-09-18 Marie Adrien Eybert Process for the treatment of fungal and microbial diseases of plants
FR2090369A1 (en) * 1970-05-29 1972-01-14 Henkel & Cie Gmbh
JPS53113025A (en) * 1977-02-16 1978-10-03 Mitsubishi Gas Chem Co Inc Proliferation inhibitor for microorganisms
US4518585A (en) * 1978-05-01 1985-05-21 Sterling Drug Inc. Hydrogen peroxide disinfecting and sterilizing compositions
JPS6142600A (en) * 1984-08-06 1986-03-01 花王株式会社 Fungicidal composition
JPS61158907A (en) * 1985-01-07 1986-07-18 Kao Corp Mildew-removing agent composition
US4900721A (en) * 1986-06-09 1990-02-13 Henkel Kommanditgesellschaft Auf Aktien Disinfectants and their use for disinfecting the skin and mucous membrane
EP0252278A2 (en) * 1986-06-09 1988-01-13 Henkel Kommanditgesellschaft auf Aktien Disinfecting agents and their use in disinfecting the skin and mucous membranes
WO1992007465A1 (en) * 1988-05-02 1992-05-14 Lester Technologies Corporation Microbiocidal combinations of materials and their use
EP0347731A2 (en) * 1988-06-18 1989-12-27 Helmut Schätzlein Process for controlling plant pests, particularly on vines, hop stems or the like
JPH02115104A (en) * 1988-10-21 1990-04-27 Sakae Funamizu Sterilizing and controlling agent against blight of tree and using thereof
US5079868A (en) * 1990-06-25 1992-01-14 Union Oil Company Of California Plant treatment with urea peroxide
US5130124A (en) * 1991-05-01 1992-07-14 Isp Investments Inc. Stabilized, aqueous, film-forming antimicrobial compositions of hydrogen peroxide
EP0524150A1 (en) * 1991-07-19 1993-01-20 Ciba-Geigy Ag Improvement in hydrogen peroxide disinfection solutions
JPH05213686A (en) * 1992-01-31 1993-08-24 Gold Kosan Kk Plant physiological activity accelerator for greenhouse culture
JPH06121619A (en) * 1992-10-12 1994-05-06 Gold Kosan Kk Method for agrichemical-free culture

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 78-80910A [45] *
DATABASE WPI Derwent World Patents Index; AN 93-299500 [38] *
DATABASE WPI Week 8615, Derwent World Patents Index; AN 86-097589 [15] *
DATABASE WPI Week 8635, Derwent World Patents Index; AN 86-228969 [35] *
DATABASE WPI Week 9023, Derwent World Patents Index; AN 90-175241 [23] *
PATENT ABSTRACTS OF JAPAN vol. 18, no. 410 (C - 1232) 2 August 1994 (1994-08-02) *
S.S.BLOCK: "Disinfection, Sterilization, and Preservation", LEA & FEBIGER, PHILADELPHIA, US *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6024986A (en) * 1999-05-24 2000-02-15 Ecolab Inc. Method of protecting growing plants from the effects of plant pathogens
WO2013096814A1 (en) * 2011-12-22 2013-06-27 Bui Huyen Phuong Non-corrosive stable peracetic acid concentrate solution
WO2020025816A1 (en) * 2018-08-03 2020-02-06 Compagnie Pour Le Haut Commerce Citrate perhydrates and uses thereof
FR3084560A1 (en) * 2018-08-03 2020-02-07 Compagnie Pour Le Haut Commerce CITRATES PERHYDRATES AND THEIR USES
CN113347884A (en) * 2018-08-03 2021-09-03 维兰肯公司 Citrate perhydrate and uses thereof
US20210298301A1 (en) * 2018-08-03 2021-09-30 Compagnie Vranken Citrate perhydrates and uses thereof
JP2021533205A (en) * 2018-08-03 2021-12-02 コンパニ ヴランケン Sodium percarbonate citrate and its use
EP3970496A1 (en) * 2018-08-03 2022-03-23 Compagnie Vranken Citrate perhydrates and uses thereof
US11737461B2 (en) * 2018-08-03 2023-08-29 Biorem Engineering Sa Citrate perhydrates and uses thereof
IL280542B1 (en) * 2018-08-03 2024-01-01 Cie Vranken Citrate perhydrates and uses thereof
IL280542B2 (en) * 2018-08-03 2024-05-01 Cie Vranken Citrate perhydrates and uses thereof

Also Published As

Publication number Publication date
FR2718924B1 (en) 1996-06-07
FR2718924A1 (en) 1995-10-27

Similar Documents

Publication Publication Date Title
FR2728143A1 (en) AQUEOUS COMPOSITION BASED ON H2O2, ACIDS AND AG, PROCESS FOR PREPARATION AND USE IN THE FIELD OF DISINFECTION AND / OR HYGIENE
EP0307992B1 (en) Compositions containing biosynthetic pesticidal products, process for their preparation and their use
EP1896045B1 (en) Composition comprising brassicacea seeds meal and their use as biopesticides in plants
BE1023957A9 (en) LIMONENE: FORMULATION AND INSECTICIDE USE
EP1048211A1 (en) Phytosanitary treatment of plants and compositions usable therefor
EP0401059B1 (en) Plant-protecting composition, process for its preparation and its use, particularly for controlling downy vine mildew
WO1995028840A1 (en) Hydrogen peroxide composition formulated for the preventive and curative treatment of diseases affecting the foliage and aerial parts of plants
EP1355532B1 (en) Fungicidal composition based on potassium acid phosphite
FR2634103A1 (en) Process and product permitting the eradication of insect pests and accelerating the development of the treated plants
WO2021123681A1 (en) Composition comprising potassium bicarbonate and use for treating and/or protecting crops
EP3211999B1 (en) Use of bismuth subsalicylate or one of the derivatives thereof as a phytopharmaceutical agent
EP1115288B1 (en) Fungicide compositions
FR2567364A1 (en) PROCESS FOR INHIBITING THE GROWTH OF AXILLARY BUDGETS BY TREATMENT WITH DIMETHYL 2,3,5,6-TETRACHLOROTEREPHTHALATE
EP4358721A1 (en) Composition comprising potassium bicarbonate and use thereof for treating and/or protecting crops
WO2023170178A1 (en) Phytosanitary composition and use thereof
BE1003881A5 (en) Method of inhibiting germination potatoes.
FR2573624A1 (en) AGENT FOR COMBATING BACTERIA AND PHYTOPATHOGENIC FUNGI COMPRISING QUATERNARY AMMONIUM COMPOUNDS
WO2021089967A1 (en) Combined preparation and method for combating fungus-growing ants
EP0392928B1 (en) Process for controlling Eudemis and Cochylis of vines, using a nuclear polyhedrosis virus
FR2780613A1 (en) Composition for application to chlorophyl-containing algae or plants comprising endothall, ammonium salt, glutamine synthetase inhibitor and surfactant
FR2614180A1 (en) FUNGICIDE BIOCIDAL COMPOSITION AND PROCESS FOR TREATING HARVESTS.
FR2471142A1 (en) FUNGICIDE COMPOSITION FOR AGRICULTURE AND HORTICULTURE AND METHOD FOR CONTROLLING FUNGI OR MYCETA
FR2760941A1 (en) Fungicidal composition for plant protection
FR2605847A1 (en) Herbicidal compositions based on aminotriazole and a derivative of 2-nitro-5-phenoxy-substituted benzoic acid, method for treating weeds using these compositions
FR2567718A1 (en) SYNERGISTIC HERBICIDE COMPOSITION BASED ON ETHOXY-2-CHLOROACETAMIDE DERIVATIVES AND 4-TRIFLUOROMETHYL-BENZENE DERIVATIVES

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i

Free format text: PAT.BUL.47/95 UNDER INID (51) "IPC", REPLACE THE EXISTING SYMBOLS BY "A01N 59/00 //(A01N 59/00, 43:76, 25:30, 25:24, 25:22)"

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase