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WO1997007675A1 - Produits et procedes permettant la liberation prolongee d'ingredients actifs en agriculture - Google Patents

Produits et procedes permettant la liberation prolongee d'ingredients actifs en agriculture Download PDF

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Publication number
WO1997007675A1
WO1997007675A1 PCT/GB1996/002074 GB9602074W WO9707675A1 WO 1997007675 A1 WO1997007675 A1 WO 1997007675A1 GB 9602074 W GB9602074 W GB 9602074W WO 9707675 A1 WO9707675 A1 WO 9707675A1
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WO
WIPO (PCT)
Prior art keywords
water
polymer
active ingredient
composition according
soluble
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.)
Ceased
Application number
PCT/GB1996/002074
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English (en)
Inventor
Simon Alexander Hanson Rose
Peter Chamberlain
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ciba Specialty Chemicals Water Treatments Ltd
Original Assignee
Allied Colloids Ltd
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 Allied Colloids Ltd filed Critical Allied Colloids Ltd
Priority to IL12336896A priority Critical patent/IL123368A0/xx
Priority to AU68289/96A priority patent/AU707743B2/en
Priority to EP96928562A priority patent/EP0852462A1/fr
Publication of WO1997007675A1 publication Critical patent/WO1997007675A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • 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
    • A01N25/08—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 solids as carriers or diluents
    • 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
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/40—Fertilisers incorporated into a matrix

Definitions

  • This invention relates to the sustained release of agricultural (including horticultural) active ingredients to plants as a result of contacting water that is to be used for irrigation of the plants with sustained release compositions which release the horticultural or other agricultural active ingredients over a prolonged period.
  • water In regions where there is inadequate rainfall, or in artificially covered growth areas such as greenhouses, it is conventional to promote the growth of plants by conducting an irrigation process in which water is flowed to the plants or to the substrate in which the plants are growing or are to be grown. Thus the water may be sprayed over the plants or it may be applied to the soil or other substrate (for instance a soiless compost) .
  • NPK fertilisers Conventional nutrient fertilisers such as NPK fertilisers are made available to the plants either by incorporation of the powder fertiliser in the substrate or, more usually, by dissolving the required amount of fertiliser in the irrigation water merely by mixing the fertiliser with the water.
  • specialised and trace active ingredients such as trace elements, chelates of pesticides in this manner since they are usually required in very low concentrations over prolonged periods, and it is not practicable to achieve this by direct distribution of the active ingredient into the irrigation water.
  • the active ingredient is absorbed into a thermoplastic microporous carrier.
  • the plant nutrient is impregnated into a polyurethane foam or other porous substrate.
  • the active ingredient is incorporated into a matrix formed from an amylaceous melt.
  • Thermoplastic or thermosetting polymer eg polyethylene
  • Such processes have the disadvantage that they leave an insoluble residue, which has to be removed or else it contaminates the growing area.
  • GB 1,598,458 the nutrient is included in microcapsules which are bonded into tablets using a wax matrix.
  • the matrix will release the nutrient but the release of the nutrient from the microcapsules will depend upon the structure of the icrocapsule shell, and this requires careful control of the manufacture of the microcapsules.
  • sustained release systems for a variety of other active ingredients are, of course, well known and include various mechanisms for controlling the rate of degradation or release of various cast, compression molded or other products. Examples include US 4,927,636, 4,911,858 and 5,188,755. However none of these are concerned with the particular problems of sustained release of specialised agricultural ingredients and none afford the opportunity of achieving this sustained release using a product which can be wholly soluble or dispersible in water, easy to manufacture with a high active content and capable of giving controlled release over prolonged periods.
  • the use of erodible blocks to supply water treatment chemicals into a flowing stream is well known.
  • the object of the invention is to provide a system for the sustained release of specialised trace agricultural active ingredients from a composition which can have a relatively high loading of the active ingredient and which is relatively easy and cheap to manufacture and which can be eroded completely away so that no undesirable residues are left when the release of the active ingredient terminates.
  • compositions that will provide the desired release over prolonged periods when included in whatever irrigation process is convenient for the particular plants involved, for instance drip irrigation or flooding irrigation. None of the proposals discussed above meet these objectives.
  • An irrigation process according to the invention for promoting the growth of plants comprises contacting water with a composition which releases agricultural active ingredient into the water and then applying this water to the plants or to a substrate in which the plants are grown or to be grown, wherein the composition is a sustained release composition comprising a solid matrix of a water- soluble wax through which is dispersed a water-soluble or water-dispersible agricultural active ingredient selected from trace elements, chelates and pesticides, and an erosion-inhibiting amount of particles of a water-soluble, gel-blocking, synthetic polymer.
  • a sustained release composition according to the invention comprises a solid matrix of a water-soluble wax through which is dispersed a water-soluble or water- dispersible active ingredient selected from trace elements, chelates and pesticides, and an erosion-inhibiting amount of particles of water-soluble, gel-blocking, synthetic polymer.
  • the amount and type of the gel-blocking polymer which is required for any particular process will depend in part on the nature of the contact between the composition and the water. The contact is generally achieved by flowing the water over the composition either continuously or intermittently and the rate of erosion will be selected according to the turbulence and duration of the flow.
  • One preferred irrigation process of the invention is drip irrigation in which the composition is positioned in or on the substrate and the irrigation water is dripped on to it.
  • This method is particularly preferred for the irrigation of trees, shrubs and vines for example in Israel and the USA.
  • a block (such as a tablet) of the composition may be placed adjacent each plant and the irrigation water may be dripped on to the block.
  • water is occasionally flooded through a growth area and the composition may be distributed as blocks throughout the flood area (eg adjacent to each tree) so as to dissolve gradually during flooding.
  • This is a preferred method for example with citrus trees in South Africa and field crops in Spain.
  • water is run down furrows which are adjacent to lines of growing plants.
  • the composition may be placed at the top of each furrow. This method is used for example in the USA,
  • irrigation water may be sprayed onto plants or a substrate. Examples of this type of process are Centre Pivot and Wheel line irrigation (used in Saudi Arabia and the USA) .
  • spray irrigation the composition is sited as a block at a convenient location in the water supply.
  • water may be stored in a tank or holding area having an inlet and an outlet and from which the irrigation water flows (eg by draining or pumping) intermittently or continuously and the composition can be located in the holding area or its inlet or outlet.
  • the invention is of particular value when the irrigation water is applied in excess, thereby saturating the substrate with water with the consequential risk of losing active ingredient in the excess water which drains from the substrate.
  • the agricultural active ingredient may be any of the conventional specialised agricultural (including horticultural) active ingredients which need to be applied in small quantities over prolonged periods and which can thus be summarised as comprising trace elements, chelates and pesticides.
  • the water-soluble or water-dispersible agricultural active ingredient is usually present in the composition as a dispersion of particulate active ingredient in the wax matrix.
  • the active ingredient should therefore preferably be capable of being present in particulate, water-soluble or water-dispersible form.
  • Suitable water-soluble or water-dispersible powders which can be used in the invention are pesticides, by which we include materials such as insecticides, fungicides, acaracides, nematocides and herbicides.
  • Trace element nutrients include molybdenum (for instance as sodium or ammonium molybdate) and boron (for instance as borax, boric acid or sodium tetraborate).
  • Metal chelates may be chelates of, for instance, zinc, iron, magnesium, manganese, copper, calcium or cobalt or various mixtures of these. Any of the conventional metal chelates used in agriculture (including horticulture) can be used in the invention. Examples of common chelating agents are ethylenediamine tetraacetic acid, hydroxyethylethylene diamine triacetic acid, diethylenetriamine penta acetic acid, ethylenediamine d i h y d r o x y p h e n y l a c e t i c a c i d , ethylenediaminedihydroxymethylphenylacetic acid and ethylenedia inedihydroxysulphonylphenylacetic acid.
  • Products containing a trace element and/or a chelate and/or a pesticide with other agriculturally useful active ingredient may be used as the active ingredient in the compositions of the invention.
  • Blends of the trace element or pesticide with other materials may be used, for instance blends of metal chelate with phosphate or phosphonate may be used when, as is conventional, it is desired to administer the chelate and phosphate simultaneously to the plant or substrate.
  • the active ingredient is merely dispersed in the wax matrix, without the water-soluble, gel-blocking, polymer adequate control of release from the wax matrix cannot easily be achieved. If the matrix has high solubility then very rapid release will occur and if it has low solubility, for instance as a result of including hydrophobic wax material, then release may be uncontrollably slow and residual material may remain in the irrigation stream. This can be undesirable and may result in problems such as blockage of spray nozzles in spray irrigation processes.
  • the rate of release of the agricultural active ingredient to the plant is controlled very easily merely by including an appropriate amount of particles of water-soluble gel-blocking synthetic polymer within the matrix.
  • the wax can be any water-soluble substance or mixture which provides a water-soluble solid matrix at ambient temperatures but which can be melted at higher temperatures. Usually the melting point of the wax is above 30°C and often above 40°C.
  • the wax may consist of a single material or a blend of materials, for instance a blend of waxes. Minor amounts of solvent or surfactant or other non-wax material may be incorporated in the wax matrix.
  • the matrix is formed of a material such as a polyethylene glycol (for example PEG 1450, PEG 4000 or PEG 8000), a polyethylene glycol ester (e.g., PEG 8000 distearate), a fatty acid (e.g., stearic acid or sodium, ammonium or other stearic acid or fatty acid salt), a fatty acid amide (e.g., stearic acid diethanolamide) or a fatty alcohol.
  • a polyethylene glycol for example PEG 1450, PEG 4000 or PEG 8000
  • a polyethylene glycol ester e.g., PEG 8000 distearate
  • a fatty acid e.g., stearic acid or sodium, ammonium or other stearic acid or fatty acid salt
  • a fatty acid amide e.g., stearic acid diethanolamide
  • Gel blocking is the mechanism which is known to be liable to occur whenever a sufficiently high molecular weight water-soluble synthetic polymer powder is added to water, unless precautions are taken to avoid it. It arises because the surface of the synthetic polymer particles starts dissolving and then forms a gel layer which tends to protect the incompletely dissolved polymer from further dissolution and tends to cause the formation of aggregates of partially dissolved polymer particles.
  • the gel blocking effect which arises with high molecular weight synthetic water-soluble polymers is considered undesirable but in the invention we make use of it to control the rate of erosion of the wax matrix.
  • the water-soluble, gel-blocking, polymer appears to achieve the desired control of dissolution rate by providing a gel- blocking effect around the surface of the matrix and accordingly the polymers which are suitable are those which have the capacity to cause gel-blocking. Whether or not a polymer has this capacity can easily be determined merely by adding finely divided polymer (eg below 200 ⁇ m) rapidly onto a small surface area of water. If this test shows that the polymer tends to hydrate to give swollen, mainly discrete gel particles then the polymer is not suitable as a gel-blocking polymer.
  • Example 3 A suitable gel blocking test is shown in Example 3 below and the preferred synthetic polymers for use in the invention are those which give a gel blocking value of at least 8, and preferably at least 10 and most preferably 12 to 20 or higher in that test.
  • the gel-blocking effect is due to a synthetic polymer since this can be manufactured to a reproducible and consistent standard, thus permitting the formulation of sustained release compositions having predictable sustained release properties.
  • the synthetic polymer must be water-soluble in the sense that it is eventually completely eroded away by the irrigation water.
  • the synthetic polymer is generally a polymer which has been formed by addition polymerisation of ethylenically unsaturated monomer wherein the monomer is either a water- soluble monomer or monomer blend or is a water insoluble monomer and the polymer is subsequently solubilised or otherwise modified.
  • hydrolysed polyvinyl acetates i.e., polyvinyl alcohol
  • polyvinyl alcohol can be used especially when they are chemically modified by carboxylation.
  • the preferred polymers are polymers of water-soluble ethylenically unsaturated monomer or monomer blends. These can be non-ionic but ionic monomers or monomer blends (for instance 5-95% ionic and 95-5% non-ionic) tend to increase gel-blocking capacity and so are usually preferred.
  • Any ionic monomer can be cationic, for instance diallyldi ethyl ammonium chloride or dialkyaminoalkyl
  • (meth) -acrylate or methacrylate as acid addition or quaternary ammonium salt for instance quaternised dimethylaminoethyl acrylate.
  • any ionic monomer is anionic
  • Anionic monomer that can be used can be any of the conventional anionic ethylenically unsaturated carboxylic or sulphonic monomers, such as sodium AMPS (US trade mark) .
  • the carboxylic monomers are generally preferred and the use of sodium acrylate (or other acrylic acid salt) is convenient.
  • Acrylamide is the preferred non-ionic monomer, but water-soluble non-ionic monomers can be used.
  • the intrinsic viscosity of the polymer is a contributing factor which influences its gel-blocking characteristics.
  • Preferred anionic polymers often have intrinsic viscosity in the range 10 to 30 dl/g, and suitable cationic polymers have intrinsic viscosities in the range 6 to 15 dl/g. However polymers with IV values of 4 or less can be used. All intrinsic viscosities are measured by suspended level viscometer in IN sodium chloride solution buffered to pH 7 at 25°C.
  • the polymer is usually formed in the absence of any added cross-linking agent but if desired a small amount of cross linking agent can be included in the monomers from which the polymer is formed so as to render the polymer highly branched and to impart greater gel-blocking tendency than the corresponding polymer made in the absence of cross-linking agent.
  • the intrinsic viscosity of the resultant polymer may not then be capable of accurate measurement but if an apparent IV can be measured it should be within the ranges given above.
  • the polymerisation conditions are preferably such that the IV would be within the ranges given above if the cross-linker had been omitted.
  • the polymer is preferably present in the wax matrix in the form of particles having a size at least 90% by weight above lO ⁇ m and generally above 50 ⁇ m.
  • the particles can be coarse, for instance up to 1mm but generally at least 90% by weight are below 800 ⁇ m and preferably below 300 ⁇ m or 200 ⁇ m. It is particularly preferred that at least 90% by weight of the particles should be below 100 or 150 ⁇ m, and in particular the particles can be fines recovered from a reverse phase or gel polymerisation process.
  • the polymer particles can be made by conventional techniques such as gel polymerisation followed by comminution and drying (and often fractionation) but it is particularly preferred that the particles should be made by reverse phase polymerisation.
  • the preferred particles are fine beads made by reverse phase bead polymerisation of aqueous monomer droplets in a non-aqueous liquid followed by drying and recovering the fine beads (often as a fraction separated from coarser beads) from the non-aqueous liquid.
  • polymer particles below lO ⁇ m made by reverse phase emulsion polymerisation generally followed by dehydration to form a substantially dry dispersion of very small particle in non-aqueous liquid, typically having a size 90% between 0.01 or 0.05 ⁇ m and 3 or 5 ⁇ m.
  • the preferred way of making the composition of the invention is by forming a melt dispersion of the particulate polymer and the active ingredient in a melt of the wax and converting the melt dispersion into the desired shape of the agricultural composition and cooling.
  • the particles are made by reverse phase polymerisation it is also possible to make the melt dispersion by forming a substantially anhydrous reverse phase dispersion of the polymer particles in a volatile organic liquid by conventional techniques, mixing the wax into the organic liquid and evaporating the organic liquid by distillation at a temperature above the melting point of the wax.
  • the melt dispersion is cooled and shaped into the desired agricultural composition.
  • composition can be cast as a large cooled block and then cut to size or it can be cast or extruded or otherwise shaped into the desired final size and cooled before, during or after the shaping.
  • the composition is usually in the form of blocks which can be small or large.
  • Small blocks which can be referred to as tablets or granules, typically have mean diameters of lOO ⁇ m to 4mm and are suitable for use when they are be scattered, for instance by hand or by a fertiliser spreader.
  • Larger blocks typically have volume of 10ml to 21 and are suitable for localised release (eg adjacent a tree) or when prolonged release is required.
  • the proportions of wax, polymer particles and active ingredient will influence the ease of manufacturing self- sustaining blocks or tablets and the rate of release. It is generally necessary that the amount of wax is in the range 30 or 35%, preferably at least 40% and often around 45 to 60%, by weight of the total block. If the amount is reduced it can be difficult to make a self-sustaining block, and if the amount is increased it can be difficult to achieve both controlled release and a sufficient amount of active ingredient.
  • the amount of polymer particles will be selected having regard to the particular polymer and the other components so as to achieve the desired amount of gel blocking.
  • the amount is generally in the range 15 to 50%, preferably around 15 to 40% by weight of the total composition. If the amount is below 15% it is difficult to achieve adequate gel blocking and control of release. If the amount is too much then the rate of release, and the amount of active ingredient which is to be released, can be undesirably low. Often the amount is not more than 30%.
  • the amount of active ingredient is generally in the range 1 to 50%. For instance amounts of 1-10% are preferred for trace elements and 20 to 40% for chelates. If the amount is too high it can be difficult to form a self-sustaining composition and to achieve controlled release of the active ingredient.
  • a preferred composition according to the invention comprises a multi ⁇ part block wherein one part is a casing or an upper layer which is contacted initially by the water and, after erosion of this part, exposes the core or a lower part.
  • the core or lower part is formed of a composition according to the invention and the outer or upper part is formed of a composition which provides more rapid release of the nutrient or other active ingredient.
  • This part can consist solely of the nutrient, bonded to the block by wax or other suitable water-soluble binder, or can consist of a dispersion of the nutrient in a wax matrix which optionally contains particles of water-soluble gel blocking polymer in proportions and using materials such as to give faster release than from the core part.
  • the following are examples of the invention.
  • a block was formed by melting together 0, 20 or 40 parts polymer, 20 parts of a proprietary iron chelate under the trade name Libfer SP and the balance, to 100 parts by weight, PEG 4000. The blending was conducted while the PEG 4000 was molten and the product was then cast into a block having a size of lOg and cooled. 80g soil was placed in a 10cm diameter pot, one block was placed on top of this and a further 50g soil was placed above it. The soil was then irrigated and the amount of iron chelate in the water which runs from the pot in the irrigation was measured. The irrigation was repeated 15 times, and the cumulative amount of iron leached for the irrigations was determined.
  • the polymer A used in this experiment was a reverse- phase bead copolymer of 70% acrylamide and 30% sodium acrylate having intrinsic viscosity 13 dl/g having size 100% below 125 ⁇ m.
  • Polymer B is a copolymer of 70% acrylamide, 30% sodium acrylate with IV 24 dl/g.
  • Polymer C is a copolymer of 60% acrylamide, 40% 2-Acrylamido-2 methyIpropane sulphonic acid as sodium salt with IV 18 dl/g. Both products had a similar particle size of 100% ⁇ 200 ⁇ m.
  • Polymers B and C were preparing using a gel polymerisation process. The results are ⁇ hown in Table 1 in which the first horizontal line is the number of irrigations and the others are the cumulative % of iron leached from the block.
  • 20g blocks were prepared by blending 50 parts molten PEG 4000, 30 parts iron chelate (Libfer SP) and 20 parts polymer fines having a size mainly in the range 10 to 200 ⁇ m to form a 20g block.
  • molten PEG 4000 30 parts iron chelate (Libfer SP)
  • 20 parts polymer fines having a size mainly in the range 10 to 200 ⁇ m to form a 20g block.
  • Polymer D is very lightly cross-linked.
  • Polymer H is a gel polymer containing 30% NaAc and 70% Acm with IV 24.
  • Polymer I is a gel polymer containing 100% NaAc with IV 13.
  • Polymer J is a gel polymer containing 95% NaAc and 5% Acm with IV 16.
  • Polymer K is a bead polymer containing 3% DMAEAqMeCl and 88% Acm with IV 7.
  • a glass funnel having a stem of 100 mm length and 7.5 mm internal diameter is positioned with the bottom of the stem 60 mm above the surface of 600 ml tap water in a 1 litre beaker. 3.0 g of the powdered polymer under test is put into the funnel while the bottom of the stem is closed with a finger. The finger is removed (whereby the powder drops onto a small area of the water) and timing is started. After 1 minute the beaker is removed and the contents are rapidly poured through a 4 mm mesh sieve above a 5 litre plastic beaker. The sieve is bounced on the top of the beaker for 30 seconds whereby polymer solution and slurry of individual particles will pass through the sieve but the sieve will retain any gel blocked polymer aggregates. The weight of wet gel (in grams) remaining on the sieve is then measured and is the gel-block value of that polymer. The process is repeated sufficient times to give 95% confidence limits.
  • Potting compost was treated with lime (20 g/1) in order to induce iron deficiency in subsequently cultivated plants.
  • Two maize seeds were planted in each 180 mm diameter pot (containing 715 g of limed compost) .
  • the maize was grown under standard conditions until nine true leaves were present, at which time chlorosis was clearly visible.
  • Pots were treated with either no iron chelate, standard iron chelate or an equivalent amount of iron chelate formulated within a slow release block.
  • the block tested contained 50 parts PEG 4000, 30 parts Libfer SP and 20 parts Polymer A from Example l.
  • the maize was assessed visually eight days after treatment. Vigour (resistance to chlorosis) was assessed against maize grown under standard conditions in un-limed compost the results were expressed as a percentage of the vigour in the un-limed control.
  • Control 70 70 65 68.3

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

Abstract

Libération prolongée d'un ingrédient actif en agriculture, choisi parmi des oligo-éléments, des chélates et des pesticides, qui est obtenue par mise en contact de l'eau d'irrigation avec une matrice solide de cire hydrosoluble à travers laquelle est dispersé l'ingrédient actif et qui comporte également une quantité inhibant l'érosion de particules de polymère synthétique, hydrosolubles et à blocage par formation de gel.
PCT/GB1996/002074 1995-08-31 1996-08-23 Produits et procedes permettant la liberation prolongee d'ingredients actifs en agriculture Ceased WO1997007675A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
IL12336896A IL123368A0 (en) 1995-08-31 1996-08-23 Products and processes for the sustained release of agricultural active ingredients
AU68289/96A AU707743B2 (en) 1995-08-31 1996-08-23 Products and processes for the sustained release of agricultural active ingredients
EP96928562A EP0852462A1 (fr) 1995-08-31 1996-08-23 Produits et procedes permettant la liberation prolongee d'ingredients actifs en agriculture

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9517708.5A GB9517708D0 (en) 1995-08-31 1995-08-31 Irrigation processes and polymeric materials for use in these
GB9517708.5 1995-08-31

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Publication Number Publication Date
WO1997007675A1 true WO1997007675A1 (fr) 1997-03-06

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PCT/GB1996/002074 Ceased WO1997007675A1 (fr) 1995-08-31 1996-08-23 Produits et procedes permettant la liberation prolongee d'ingredients actifs en agriculture

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EP (1) EP0852462A1 (fr)
AU (1) AU707743B2 (fr)
CA (1) CA2227926A1 (fr)
GB (1) GB9517708D0 (fr)
IL (1) IL123368A0 (fr)
WO (1) WO1997007675A1 (fr)
ZA (1) ZA967288B (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998057531A1 (fr) * 1997-06-18 1998-12-23 Ciba Specialty Chemicals Water Treatments Limited Procede d'irrigation
WO2004066728A1 (fr) * 2003-01-29 2004-08-12 Pestalto Environmental Products Inc. Compositions permettant la liberation controlee de produits antiparasitaires dans des environnements aquatiques
WO2006021708A1 (fr) * 2004-08-06 2006-03-02 Snf S.A.S. Granules d'engrais et procede de fabrication
US9206381B2 (en) 2011-09-21 2015-12-08 Ecolab Usa Inc. Reduced misting alkaline cleaners using elongational viscosity modifiers
US9637708B2 (en) 2014-02-14 2017-05-02 Ecolab Usa Inc. Reduced misting and clinging chlorine-based hard surface cleaner
WO2017103301A1 (fr) * 2015-12-16 2017-06-22 Enersos I, S.L. Particules métalliques polymères pour la production de biogaz
US10370626B2 (en) 2016-05-23 2019-08-06 Ecolab Usa Inc. Reduced misting acidic cleaning, sanitizing, and disinfecting compositions via the use of high molecular weight water-in-oil emulsion polymers
US10392587B2 (en) 2016-05-23 2019-08-27 Ecolab Usa Inc. Reduced misting alkaline and neutral cleaning, sanitizing, and disinfecting compositions via the use of high molecular weight water-in-oil emulsion polymers
ES2823927A1 (es) * 2019-11-07 2021-05-10 Beijing Enbiwo Biological Tech Co Ltd Composición en tamaño micrométrico y su uso como agente coadyuvante de alcaloides vegetales
US11540512B2 (en) 2017-03-01 2023-01-03 Ecolab Usa Inc. Reduced inhalation hazard sanitizers and disinfectants via high molecular weight polymers
US11834633B2 (en) 2019-07-12 2023-12-05 Ecolab Usa Inc. Reduced mist alkaline cleaner via the use of alkali soluble emulsion polymers

Citations (5)

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US3980462A (en) * 1973-07-27 1976-09-14 Bayer Aktiengesellschaft Fertilizer for long term supply of plants with chelated micronutrients
US4299613A (en) * 1979-02-22 1981-11-10 Environmental Chemicals, Inc. Controlled release of trace nutrients
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AU734331B2 (en) * 1997-06-18 2001-06-14 Ciba Specialty Chemicals Water Treatments Limited Irrigation method
WO1998057531A1 (fr) * 1997-06-18 1998-12-23 Ciba Specialty Chemicals Water Treatments Limited Procede d'irrigation
WO2004066728A1 (fr) * 2003-01-29 2004-08-12 Pestalto Environmental Products Inc. Compositions permettant la liberation controlee de produits antiparasitaires dans des environnements aquatiques
US7563453B2 (en) 2003-01-29 2009-07-21 Pestalto Environmental Products Compositions for controlled release of pest control products in aquatic environments
WO2006021708A1 (fr) * 2004-08-06 2006-03-02 Snf S.A.S. Granules d'engrais et procede de fabrication
AU2005276323B2 (en) * 2004-08-06 2009-03-26 Snf S.A.S. Fertilizer granules and method for making same
US7931728B2 (en) 2004-08-06 2011-04-26 Snf S.A.S. Fertilizer granules and manufacturing process
US9206381B2 (en) 2011-09-21 2015-12-08 Ecolab Usa Inc. Reduced misting alkaline cleaners using elongational viscosity modifiers
US10821484B2 (en) 2014-02-14 2020-11-03 Ecolab Usa Inc. Reduced misting and clinging chlorine-based hard surface cleaner
US9637708B2 (en) 2014-02-14 2017-05-02 Ecolab Usa Inc. Reduced misting and clinging chlorine-based hard surface cleaner
US11331696B2 (en) 2014-02-14 2022-05-17 Ecolab Usa Inc. Reduced misting and clinging chlorine based hard surface cleaner
US10220421B2 (en) 2014-02-14 2019-03-05 Ecolab Usa Inc. Reduced misting and clinging chlorine-based hard surface cleaner
CN108473351A (zh) * 2015-12-16 2018-08-31 安尔索思I有限责任公司 用于生产沼气的聚合物金属颗粒
WO2017103301A1 (fr) * 2015-12-16 2017-06-22 Enersos I, S.L. Particules métalliques polymères pour la production de biogaz
US10392587B2 (en) 2016-05-23 2019-08-27 Ecolab Usa Inc. Reduced misting alkaline and neutral cleaning, sanitizing, and disinfecting compositions via the use of high molecular weight water-in-oil emulsion polymers
US10370626B2 (en) 2016-05-23 2019-08-06 Ecolab Usa Inc. Reduced misting acidic cleaning, sanitizing, and disinfecting compositions via the use of high molecular weight water-in-oil emulsion polymers
US11008538B2 (en) 2016-05-23 2021-05-18 Ecolab Usa Inc. Reduced misting alkaline and neutral cleaning, sanitizing, and disinfecting compositions via the use of high molecular weight water-in-oil emulsion polymers
US11540512B2 (en) 2017-03-01 2023-01-03 Ecolab Usa Inc. Reduced inhalation hazard sanitizers and disinfectants via high molecular weight polymers
US11834633B2 (en) 2019-07-12 2023-12-05 Ecolab Usa Inc. Reduced mist alkaline cleaner via the use of alkali soluble emulsion polymers
US12281286B2 (en) 2019-07-12 2025-04-22 Ecolab Usa Inc. Reduced mist alkaline cleaner via the use of alkali soluble emulsion polymers
ES2823927A1 (es) * 2019-11-07 2021-05-10 Beijing Enbiwo Biological Tech Co Ltd Composición en tamaño micrométrico y su uso como agente coadyuvante de alcaloides vegetales

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CA2227926A1 (fr) 1997-03-06
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AU707743B2 (en) 1999-07-15
ZA967288B (en) 1997-08-28
IL123368A0 (en) 1998-09-24
GB9517708D0 (en) 1995-11-01

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