WO2018202616A1 - Biocide encapsulé dans un alkyde - Google Patents

Biocide encapsulé dans un alkyde Download PDF

Info

Publication number
WO2018202616A1
WO2018202616A1 PCT/EP2018/061018 EP2018061018W WO2018202616A1 WO 2018202616 A1 WO2018202616 A1 WO 2018202616A1 EP 2018061018 W EP2018061018 W EP 2018061018W WO 2018202616 A1 WO2018202616 A1 WO 2018202616A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyd
emulsion
biocide
coating composition
aqueous solution
Prior art date
Application number
PCT/EP2018/061018
Other languages
English (en)
Inventor
Zoe Emily BUTTON
Bogdan-Catalin IBANESCU
Richard Barcock
Original Assignee
Akzo Nobel Coatings International B.V.
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 Akzo Nobel Coatings International B.V. filed Critical Akzo Nobel Coatings International B.V.
Priority to EP18719913.8A priority Critical patent/EP3618631A1/fr
Priority to BR112019021228A priority patent/BR112019021228A2/pt
Priority to RU2019137971A priority patent/RU2724547C1/ru
Priority to CN201880024197.9A priority patent/CN110545668A/zh
Publication of WO2018202616A1 publication Critical patent/WO2018202616A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides

Definitions

  • the present invention relates to an emulsion of an alkyd in an aqueous solution wherein the alkyd comprises a biocide, a process to prepare such an emulsion and to a coating composition comprising such an emulsion.
  • Paints such as architectural paints containing insecticides used to coat walls, floors and ceilings inside buildings are known. Such insecticidal paints usually kill insects by contact. Many of the known insecticidal paints are solvent borne, that is to say, the majority, if not all of the carrier liquid is organic solvent. This is largely because insecticides are large organic molecules that do not readily dissolve in aqueous paints, particularly at the low VOC (volatile organic content) level demanded by legislation and consumers throughout the world. [0003] Paints, comprising an insecticide (i.e. an insecticidal paint) can be made by adding the desired amount of insecticide to the final paint composition.
  • an insecticide i.e. an insecticidal paint
  • WO201364441 is disclosed that certain insecticides remain active in the dried paint film for only a short time, sometimes only a few days, resulting in dried paint films which contain no active insecticide, or at least so little that it is less than the minimum effective amount necessary to kill all or even some of the insects. Insecticides which are susceptible to leaving the dried film in this way are volatile. Interior architectural paint is normally expected to last many months and possibly a year or more. Naturally, consumers expect that the insecticidal activity of an insecticidal paint will also last a similar length of time. A way of making low VOC aqueous insecticidal architectural paints, comprising volatile insecticides is disclosed in WO201364441 .
  • encapsulation methods are known in the art e.g. matrix encapsulation wherein the active compound is dispersed in the encapsulation material (beads, microparticles, microspheres); or core / shell encapsulation wherein the active compound is confined as one core by one shell or more (multi-shell).
  • Core / shell encapsulation is sometimes also referred to as microencapsulation.
  • a microcapsule is a small sphere with a uniform wall around it. The material inside the microcapsule is referred to as the core, internal phase, or fill, whereas the wall is sometimes called a shell, coating, or membrane.
  • EP2851401 discloses a biocide composition for controlling invasive species and pests, coating products thereof and use thereof. It discloses the microencapsulation of active substances with a binder in a polymer and mineral casing.
  • the microencapsulation of active substance e.g. insecticide, is obtained using polymerization of binder in a polymer and mineral casing creating a core- shell structure around the active substance.
  • the encapsulation requires the polymerization of at least one monomer in the interphase of two immiscible substances, giving rise to a membrane that constitutes the wall of the microcapsule (core/shell encapsulation).
  • the active ingredient is dispersed uniformly throughout a continuous material (matrix) and the main release profile is sustained release where the active is slowly released over time.
  • matrix a continuous material
  • the active needs to have a very high partition coefficient (solubility) in the material.
  • the matrix of choice needs to be water insoluble and inert to other formulation components as well as the active.
  • the matrix should have a high glass transition temperature or reasonable crosslinking to allow for slow diffusion of the active out of the matrix.
  • EP201214 discloses polymeric microparticles having bound therewith a pesticide in which active substances are bound to the outer surface of microparticles.
  • Inesfly ® products use the micro-encapsulation technology, which is the key element that gives Inesfly products their special characteristics.
  • the formation of the Inesfly Technology is a chemical process which produces microcapsules in suspension.
  • These microcapsules are as a core-shell species whereby there is a core comprising the active, and a shell, wall or structure that surrounds the former, without active.
  • These microcapsules include conventional biocides at very low doses and insect growth regulators. Gradual and controlled release of the microencapsulated active ingredients is a direct result of the polymeric covering (www.inesflyafrica.com).
  • Painticide released in collaboration with the Institute for Medical Research (IMR) is an emulsion paint formulation impregnated with a pyrethroid (deltamethrin) that allows the slow release of the insecticide to the wall surface (http://www.imr.qov.my/). It discloses a "drop in" of deltamethrin into the paint formulation after which the biocide is trapped in the resulting paint formulation.
  • Many insecticides including many of the class of pyrethrins comprise one or more chiral centers and often the insecticidal activity of the insecticide differs between different enantiomers, diastereomers or epimers.
  • a problem with existing coating and/or paint compositions comprising insecticides is that due to the alkaline conditions such as in wet paint, racemization of one or more of the chiral centers may occur in the wet paint reducing the effective active concentration of the insecticide. This is especially the case with waterborne coatings compositions. To maintain a minimum level of active concentration of insecticide, a doubling of the concentration of insecticide is required for each chiral atom where racemization may occur during storage. That would increase the costs of the coating composition and may also influence coating quality. Additionally, there is a trend towards reduction of authorized active substances or reduction of levels of authorized active substances.
  • racemization of an insecticide in a waterborne paint can be reduced using a matrix-type encapsulation of the insecticide in an alkyd which reduces the racemization of an optically active insecticide.
  • the alkyd-encapsulated insecticide may be added to a coating composition and still maintain its protective environment for the insecticide in the coating composition.
  • the alkyd encapsulation prevents the insecticide from racemization or at least reduces the racemization speed.
  • the alkyd encapsulation does not prevent migration of the insecticide to the surface of the (dried) coating layer and hence allows for a prolonged activity of the insecticide. It is understood that this type of alkyd encapsulation can also be applied more generally to optically active biocides.
  • the present invention provides an emulsion of an alkyd in an aqueous solution wherein the alkyd comprises a biocide and the aqueous solution comprises between 0.1 and 10 wt% of surfactant.
  • the invention further provides a process to prepare such an emulsion and a coating composition comprising such an emulsion.
  • alkyd refers herein to polyester derived from polyols such as pentaerytritol, trimethylolpropane of propeneglycol and a dicarboxylic acid such as phthalic acid or maleic acid or carboxylic anhydride such as phthalic acid anhydride or maleic acid anhydride.
  • Alkyds may further comprise triglycerides derived from polyunsaturated fatty acids (often derived from plant and vegetable oils, e.g. linseed oil, soybean oil, sunflower oil, or safflower oil).
  • a typical alkyd resin is prepared by heating for example linseed oil, phthalic acid anhydride and glycerol to obtain a fatty-acid containing polyester.
  • Alkyds can be used in paints or coating compositions. Different levels of oil in the paint provide different paint characteristics. Alkyds and alkyd-based paints can be diluted with solvents to allow for an easier handling. Further important components of alkyd paint are pigments and extenders. The pigment is the substance that gives the paint color. Pigments are derived from natural or synthetic materials that have been ground into fine powders. Extenders are inert pigments used to extend or increase the bulk of paint. Extenders are also used to adjust the consistency of paint and to let down colored pigments of great tinting strength. The last important category of components of alkyd paint comprises the additives e.g. to accelerate paint drying.
  • Alkyds can be classified based on a wide range of properties such as oil length and acid value being, see for example Coatings Technology Handbook, Second Edition edited by D. Satas, Arthur A. Tracton pages 435-437, which is included herein by reference.
  • Oil length is defined as weight % of oil calculated on the theoretical non-volatile content of the final alkyd when condensed to the midpoint of the acid value specification: very long oil: 75% and over; long oil: between 60 and 75%; medium oil: between 45 and 60%; short oil: up to 45%.
  • Acid value is defined as the number of milligrams of potassium hydroxide required to neutralize one gram of the polymer under the conditions specified below (lUPAC definition). It is determined using a standard potassium hydroxide solution (0.1 N) in methanol and a one per cent of phenolphthalein in ethanol (95 per cent) as indicator. An ethanol— toluene mixture is prepared by mixing equal volumes of ethanol (95 per cent) and toluene and neutralized with a methanolic potassium hydroxide solution (0.1 N) in the presence of phenolphthalein as indicator. 1 -2 g of the sample is dissolved in 50 ml of the ethanol— toluene mixture. The solution is titrated with methanolic potassium hydroxide solution in the presence of pbenolphtbalein as indicator. The acid value is calculated as follows:
  • Enantiomer ratio is defined as the amount of the first enantiomer (E1 ) divided by the amount of the second enantiomer (E2), i.e. E1/E2.
  • Enantiomer fraction is defined as the amount of the first enantiomer divided by the total amount of the first and second enantiomer, i.e. E1 / (E1 + E2).
  • Enantiomer excess is defined as the absolute value of the difference in the amount of the first enantiomer and second enantiomer, i.e.
  • where E1 +E2 1 (or 100%).
  • Surfactant refers to compounds that lower the surface tension (or interfacial tension) between two liquids Surfactants may act as detergents, wetting agents, emulsifiers, foaming agents, and dispersants. Surfactants are usually organic compounds that are amphiphilic, meaning they contain both hydrophobic groups (their tails) and hydrophilic groups (their heads). Therefore, a surfactant contains both a water-insoluble (or oil-soluble) component and a water-soluble component. Surfactants will diffuse in water and adsorb at interfaces between air and water or at the interface between oil and water, in the case where water is mixed with oil.
  • the water-insoluble hydrophobic group may extend out of the bulk water phase, into the air or into the oil phase, while the water-soluble head group remains in the water phase.
  • surfactants are classified according to polar head group.
  • a non-ionic surfactant has no charged groups in its head.
  • the head of an ionic surfactant carries a net positive, or negative charge. If the charge is negative, the surfactant is more specifically called anionic; if the charge is positive, it is called cationic. If a surfactant contains a head with two oppositely charged groups, it is termed zwitterionic.
  • Anionic surfactants contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate, and carboxylates and are well-known in the art.
  • Non-ionic surfactants include many long chain alcohols which exhibit some surfactant properties e.g. fatty alcohols, cetyl alcohol (hexadecane-1 -ol or palmityl alcohol), stearyl alcohol, and oleyl alcohol.
  • Other examples of non-ionic surfactants include polyethylene glycol alkyl ethers (e.g.
  • octaethylene glycol monododecyl ether pentaethylene glycol monododecyl ether
  • polypropylene glycol alkyl ethers glucoside alkyl ethers (e.g. decyl glucoside, lauryl glucoside, octyl glucoside), polyethylene glycol octylphenyl ethers (e.g. triton X-100), polyethylene glycol alkylphenyl ethers (e.g. nonoxynol-9), glycerol alkyl esters (e.g. glyceryl laurate), polyoxyethylene glycol sorbitan alkyl esters (e.g.
  • polysorbate sorbitan alkyl esters
  • cocamide MEA sorbitan alkyl esters
  • cocamide DEA dodecyldimethylamine oxide
  • block copolymers of polyethylene glycol and polypropylene glycol polyethoxylated tallow amine (POEA), or mixtures thereof.
  • POEA polyethoxylated tallow amine
  • the median particle size can for example be measured using a Mastersizer 2000 instrument as described elsewhere herein.
  • a water-borne coating composition or waterborne paint is herein defined as a coating / paint composition wherein the amount of non-aqueous solvent is less than 15 wt%, preferably less than 10 wt%, more preferably less than 5 wt%, such as less than 4, 3, 2, or even less than 1 wt%.
  • a coating composition can be applied to the surface of an object, usually referred to as the substrate. The purpose of applying the coating may be decorative, functional, or both. The coating itself may be an all-over coating, completely covering the substrate, or it may only cover parts of the substrate.
  • Paints and lacquers are coatings that mostly have dual uses of protecting the substrate and being decorative, although some artist's paints are only for decoration, and the paint on large industrial pipes is presumably only for the function of preventing corrosion.
  • the coating composition After application of the coating composition to a substrate the coating composition dries / cures to become a dried coating film or covering of the substrate. Drying and curing of a coating occurs e.g. by evaporation of solvents and polymerization reactions between different components in the coating composition.
  • Weight percentages (wt%) of an ingredient in a composition are expressed as the weight percentage of the specific ingredient compared to the weight of the total composition.
  • Figure 1 the median particle size d(0.5) of emulsions prepared from the eight (8) different alkyds as listed in the examples containing deltamethrin at 0.5 and 1 .0 wt% (black and grey column, respectively).
  • Figure 2 Deltamethrin active isomer (%), (as a measure of stability towards racemization) in a water-based (waterborne) coating composition is shown when added as standard drop-in in white water-based wall paint in the PVC range of 20 - 80 as a function of pH.
  • Figure 3 Deltamethrin stability when encapsulated in very long oil alkyd emulsion as compared standard drop in (DMN-SC) as a function of pH.
  • Figure 4 Deltamethrin stability when encapsulated in long oil alkyd emulsion as compared standard drop in (DMN-SC) as a function of pH.
  • Figure 4A for pH 8,
  • Figure 4B for pH 9 and
  • Figure 4C for pH 10.
  • Figure 5 Deltamethrin stability when encapsulated in short and medium oil alkyd emulsion as compared standard drop in (DMN-SC) as a function of pH.
  • Figure 5A for pH 8,
  • Figure 5B for pH 9
  • Figure 6 Bio efficacy for eight variants of encapsulation of deltamethrin in alkyd number 6 compared to standard drop-in.
  • the invention relates to an emulsion of an alkyd in an aqueous solution characterized in that the alkyd comprises a biocide and the aqueous solution comprises between 0.1 and 10 wt% of surfactant. It has surprisingly been found that the racemization rate of the biocide can be reduced by dissolving it in the alkyd phase of such an emulsion. As a result, the biocide remains active for a longer period of time and a paint formulation comprising the emulsion can be prepared and stored for a longer period compared to drop in compositions.
  • the alkyd oil length may vary in the emulsion of the invention. In one aspect, the alkyd oil length is higher than 60%, preferably wherein the alkyd oil length is higher than 75%. Also mixtures of alkyds with different oil lengths may be used. [0039] In one aspect of the invention the acid value of the alkyd is between 0 and 20. In another aspect the acid value is between 0 and 15. In still another aspect the acid value is between 2 and 15. In yet another aspect it is between 2 and 10. In one aspect it is below 2, or in another aspect it is between 10 and 15. [0040] The emulsion obtained according to the invention may comprise different amounts of surfactant concentration and/or type of surfactant.
  • the surfactant is selected from one or more members of the group consisting of non-ionic surfactants and ionic surfactants; preferably the surfactant is an non-ionic surfactant.
  • the non-ionic surfactant is polyvinylalcohol of medium levels of hydrolysis (e.g. 88%) and medium molecular weight (e.g. 31000 Da). Also the amount of surfactant may be varied to steer emulsion characteristics.
  • the surfactant concentration in the emulsion obtained in the method according to the invention to encapsulated a biocide in an alkyd is between 0.1 and 10 %wt , or in another embodiment between 1 and 9%wt or between 2 and 8 %wt, or even between 3 and 7 %wt.
  • the amount of non-ionic surfactant in the emulsion obtained in the method according to the invention to encapsulated a biocide in an alkyd is between 0.1 and 10 %wt , or in another embodiment between 1 and 9%wt or between 2 and 8 %wt, or even between 3 and 7 %wt.
  • the amount of non-volatiles may vary in the emulsion of the invention.
  • the emulsion of an alkyd in an aqueous solution of the current invention comprises between 20 and 60 % non-volatiles, preferably between 35 and 50% non-volatiles. In another embodiment it is between 30 and 55 %wt. In still another embodiment it is between 40 and 50 %wt. In yet another embodiment it is between 38 and 42 %wt.
  • a problem with existing coating and/or paint compositions comprising insecticides is that due to the alkaline conditions such as in wet paint, racemization of one or more of the chiral centers may occur in the wet paint reducing the effective active concentration of the insecticide.
  • the encapsulation of a biocide in an alkyd emulsified in an aqueous solution according to the invention prevents or at least reduces racemization of the alkyd-encapsulated biocide at alkaline pH values.
  • Racemization of biocides, e.g. insecticides such as deltamethrin is known to occur under basic conditions. Under neutral conditions, the racemization rate is generally lower than under basic conditions.
  • the invention relates to an emulsion of an alkyd in an aqueous solution as herein described wherein the pH of the emulsion is between 7 and 1 1 , preferably between 8 and 10, or wherein the pH of the emulsion is between 8 and 9. In yet another embodiment it is between 7.5 and 10.5.
  • the pH of a coating composition comprising an emulsion of an alkyd in an aqueous solution as herein described is in one aspect between 7 and 1 1 , in another embodiment between 7.5 and 10.5, or even between 8 and 10, in yet another embodiment it is between 8 and 9.
  • the amount of biocide in the emulsion of an alkyd in an aqueous solution according to the current invention depends upon the type of biocide used. It is understood that biocides may have different minimum concentrations in order to be effective.
  • the invention relates to an emulsion of an alkyd in an aqueous solution of the current invention wherein the amount of biocide in the emulsion is less than 10 %wt, e.g. less than 9, 8, 7, 6, 5, 4, 3 %wt or even less than 2 %wt or less than 1 %wt. In another aspect it is between 0.001 and 10 wt% calculated from the weight of the emulsion.
  • it is between 0.001 and 6 wt%, or between 0.01 and 6 wt%, e.g between 0.01 and 5wt%, between 0.1 and 6wt%, or in yet another embodiment between 1 and 6 wt%, or in still another embodiment between 0.01 and 2 wt%, or even between 0.1 and 1 wt%. In one embodiment it is between 2 and 5 wt%.
  • the emulsion of an alkyd in an aqueous solution according to the current invention can be stored for several days such as at least 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or even at least 100 days.
  • the emulsion may be stored at room temperature.
  • the median particle size d(0.5) of the emulsion does not affect the stability of the biocide, hence in one aspect, there are no restriction on the median particle size d(0.5) of the emulsion.
  • the median particle size d(0.5) of the emulsion is below 1 .0 micron.
  • the median particle size d(0.5) of the emulsion is between 0.5 and 30 microns or in still another aspect between 1 and 1 1 microns.
  • the median particle size d(0.5) of the emulsion is between 5 and 10 microns. In a further aspect, the median particle size d(0.5) of the emulsion remains stable during storage. It is understood that larger particles in an emulsion may settle during storage, they may be redispersed using methods known in the art such as using low shear mixing.
  • the invention relates to an emulsion of an alkyd in an aqueous solution of the current invention wherein the biocide is an insecticide.
  • the insecticide is a pyrethroid or pyrethrin.
  • the class of insecticides called pyrethroids comprises insecticides such as Allethrin, Bifenthrin, Cyfluthrin, Cypermethrin, Cyphenothrin, Deltamethrin, Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, Imiprothrin, lambda-Cyhalothrin, Metofluthrin, Permethrin, Prallethrin, Resmethrin, Silafluofen, Sumithrin, tau-Fluvalinate, Tefluthrin, Tetramethrin, Tralomethrin, and Transfluthrin.
  • insecticides such as Allethrin, Bifenthrin, Cyfluthrin, Cypermethrin, Cyphenothrin, Deltamethrin, Esfenvalerate, Etofenprox, Fenpropathrin, Fenvaler
  • the insecticide is a pyrethroid; more preferably the insecticide is selected from the group consisting of permethrin, deltamethrin and cypermethrin, or combinations thereof; even more preferably the insecticide is deltamethrin.
  • Deltamethrin is a well-known insecticide that can be used in this invention because it has an chiral center that is known to racemize under alkaline conditions. Deltamethrin has a fast action against invasive species, a relative short contact period between the species and deltamethrin is sufficient to be effective, e.g. an insect landing on a substrate coated with a coating composition according to the invention can be long enough for deltamethrin to be effective against the insect.
  • the invention relates to a process for preparing the emulsion of an alkyd in an aqueous solution of the current invention, comprising the steps of: providing an aqueous solution of a surfactant comprising between
  • step ii optionally removing the solvent of step ii,
  • vii. optionally adjusting the pH of the emulsion to a value between 7 and 1 1 , preferably between 8 and 10, or to a value between 8 and 9.
  • steps ii, iii, and iv may be replaced by an alternative step of providing a biocide dissolved in an alkyd. This is particularly interesting when the solution of the desired biocide in the desired alkyd can be obtained.
  • the invention relates to the process as described above comprising the alternative step instead of steps ii, iii, and iv.
  • the invention relates to an emulsion of an alkyd in an aqueous solution obtained in this process.
  • Emulsifying an alkyd in an aqueous solution can be done by adding the aqueous solution into the alkyd, or by adding the alkyd into the aqueous solution.
  • the emulsion is prepared by adding the aqueous solution into the alkyd, or by adding the alkyd into the aqueous solution; preferably by adding the alkyd into the aqueous solution as this preparation method allows for a wider range of emulsion properties to be achieved (e.g. particle size).
  • Variation of the process parameters such as mixing time, mixing speed, rate of addition, neutralization rate, ratio between surfactants used, process temperature may influence the characteristics of the emulsion obtained.
  • the leaching rate of the active e.g. biocide or insecticide
  • the type of matrix i.e. type of alkyd
  • the particle size controlled by process parameters.
  • a decrease in diffusion coefficient which may be influence by the type of alkyd, also leads to a decrease on the amount of active leached.
  • step vi In general longer alkyds have high solids content and a low solvent content, such solvent being of an organic nature, in other words being classified as “volatile organic solvent” (VOC) which needs to be removed from the emulsion obtained in the process according to the invention (step vi).
  • VOC volatile organic solvent
  • the optional step vi "remove solvent from step ii" may be redundant, especially when the liquid content of the alkyd is low such as less than 10 wt %, preferably less than 5 wt%, or less than 4, 3, or even less than 2 wt%, the wt% being calculated on the total weight of the alkyd.
  • the emulsion of the instant invention can be added to a coating composition. It has surprisingly been found that the reduced racemization of the biocide as found in the emulsion of an alkyd in an aqueous solution characterized in that the alkyd comprises a biocide is maintained when such an emulsion is added to a coating composition. So in a further aspect, the invention relates to a coating composition comprising the emulsion of an alkyd in an aqueous solution characterized in that the alkyd comprises a biocide as herein defined. In one embodiment, the racemization of the biocide in such a coating composition is less than 50% when stored at 54°C for 3 weeks.
  • the relative amount of active enantiomer of the biocide after 3 weeks of storage at 54 °C is at least 2% higher than the relative amount of active enantiomer of the insecticide in an identical coating composition (except for alkyd-encapsulated biocide) comprising the same amount of biocide via "drop-in" after 3 weeks of storage at 54 °C.
  • the amount of biocide in such a coating composition is between 0.0001 and 5 wt%, or the amount of insecticide in such a coating composition is between 0.0001 and 5 wt%.
  • the invention relates to a coating composition
  • a coating composition comprising the emulsion of an alkyd in an aqueous solution characterized in that the alkyd comprises a biocide as herein defined, wherein the pH of the coating composition is between 7 and 1 1 , preferably between 8 and 10, or wherein the pH of the coating composition is between 8 and 9.
  • the coating composition can be a latex or another type of paint. It is water borne.
  • the racemization of the biocide in the coating composition comprising the emulsion of an alkyd in an aqueous solution characterized in that the alkyd comprises a biocide according to the invention is less than 50% when stored at 54°C for 3 weeks.
  • the racemization of the biocide is less than 45%, e.g. less than 40%, 35%, 30%, 25%, 20%, 15%, 10% or even less than 5% when stored at 54°C for 3 weeks.
  • the enantiomer excess of active enantiomer of the biocide in a coating composition comprising the alkyd encapsulated biocide according to the invention, after 3 weeks of storage at 54 °C, is at least 2% higher e.g.
  • the biocide (with a known enantiomer excess) is added to the first one in form of an alkyd-encapsulated biocide as herein described, the same amount of biocide with the same enantiomer excess is added to the second container via "drop in”. So the amount of biocide (wt%) in both containers is the same. Both containers are stored under the same conditions (closed container, mixing the alkyd through the coating composition, storage at 54°C for 3 weeks).
  • drop in of a biocide in a coating composition means that the biocide is added to the coating composition in a pure form, i.e. the pure biocide (or a solution thereof) is added drop wise to the coating composition to the desired concentration.
  • the relative amount of biocide in a coating composition comprising the alkyd-encapsulated biocide according to the invention is between 0.001 and 10 wt% of the coating composition. In another embodiment it is between 0.01 and 5 wt% of the coating composition. In one embodiment it is between 0.01 and 3 wt%. In yet another embodiment it is between 0.01 and 2.5 wt%. In still another embodiment it is between 0.05 and 5 wt% or between 0.1 and 5 wt%.
  • the relative amount of insecticide in a coating composition comprising the alkyd-encapsulated insecticide according to the invention is between 0.001 and 5 wt% of the coating composition. In one embodiment it is between 0.01 and 3 wt%. In yet another embodiment it is between 0.01 and 2.5 wt%. In still another embodiment it is between 0.05 and 2.5 wt%.
  • the amount of biocide is less than 2.5 wt%, e.g. 2.0, 1 .5 or 1 .0 wt%. Accordingly, in one embodiment the amount of biocide in the coating composition of the invention is between 0.001 and 1 .0 wt%.
  • the amount of insecticide in the coating composition of the invention is between 0.001 and 1 .0 wt%.
  • amount of deltamethrin in the coating composition of the invention is between 0.001 and 1 .0 wt%.
  • the amount of biocide in the coating composition of the inventin is between 0.0001 and 0.1 wt%.
  • the relative amount of biocide in the emulsion of an alkyd in an aqueous solution wherein the alkyd comprises a biocide according to the invention is less than 10 wt%, or in another embodiment less than 5 wt%. In another aspect it is between 0.01 and 10 wt% of the emulsion. In one embodiment it is between 0.01 and 5 wt%. In yet another embodiment it is between 0.01 and 2.5 wt%. In still another embodiment it is between 0.05 and 5 wt% or between 0.1 wt% and 5 wt % or even between 0.1 and 2.5 wt%.
  • the relative amount of insecticide in such an emulsion according to the invention is less than 10 wt%, or in another embodiment less than 5 wt%. In another aspect it is between 0.01 and 10 wt% of the emulsion. In one embodiment it is between 0.01 and 5 wt%. In yet another embodiment it is between 0.01 and 2.5 wt%. In still another embodiment it is between 0.05 and 5 wt% or between 0.1 wt% and 5 wt % or even between 0.1 and 2.5 wt%.
  • the emulsion according to the invention can be added to a coating composition to obtain a coating composition with biocide activity. It can also be used to provide biocide activity to other objects, or alternatively, the coating composition comprising the alkyd-encapsulated biocide can be applied to products such as bed nets, clothes, insect repellent nets to cover open windows or doors, or any other object one would like to have biocide activity. So in yet another aspect, the invention relates to an object comprising or soaked in or covered with the alkyd-encapsulated biocide (e.g. insecticide) obtainable / obtained with the method of the invention.
  • the biocide is an insecticide
  • the insecticide is deltamethrin.
  • the invention relates to a container comprising the emulsion of an alkyd comprising a biocide in a aqueous solution according to the invention, or in another embodiment to a container comprising a coating comprising said emultion.
  • the biocide is an insecticide
  • the insecticide is deltamethrin.
  • substrates can be coated with a coating composition comprising the emulsion of an alkyd in an aqueous solution characterized in that the alkyd comprises a biocide as herein defined, using application methods known in the art such as spraying, applying by brush or roller, soaking of the substrate in the paint, etc. Substrates can be fully coated or partially coated.
  • the substrate After drying of the coating, the substrate is covered or partially covered, by a dried coating film which has biocidal activity, e.g. insecticidal activity so that when insects touch the coated part of such a substrate, they suffer from the insecticidal activity of the insecticide present in the coating.
  • biocidal activity e.g. insecticidal activity
  • the invention relates to a substrate or part thereof, coated with such a coating composition. After curing / drying of such a coating layer, the dried coating layer slowly releases the biocide.
  • the invention also relates to a coating process comprising the step of coating a substrate with a coating composition comprising the emulsion of an alkyd in an aqueous solution characterized in that the alkyd comprises a biocide as herein defined. Substrates obtained in such a process are also part of the invention.
  • the invention relates to a substrate coated with a coating deposited from a coating composition according to the invention (i.e. comprising the emulsion of an alkyd in an aqueous solution of the invention) or to a substrate coated with an emulsion deposited from the emulsion according to the invention.
  • a coating composition according to the invention i.e. comprising the emulsion of an alkyd in an aqueous solution of the invention
  • a substrate coated with an emulsion deposited from the emulsion according to the invention i.e. comprising the emulsion of an alkyd in an aqueous solution of the invention
  • the invention relates to the use of a coating composition according the invention a varnish, lacquer, paint, coating, stain, enamel, printing ink or floor covering, preferably in a varnish, lacquer, paint, or coating.
  • the encapsulation method using direct emulsification consisted of the following steps. First a 5 % weight solution of surfactant (polyvinylalcohol with a molecular weight of 31000 g/mol and 88 mol% hydrolysis, commercial name Mowiol ® 4-88 (Sigma-Aldrich)) in water was prepared and heated to 60 °C. Separately deltamethrin (100 % purity) was added to the alkyd resin to which 10 % weight solvent (methyl ethyl ketone) had been added. The alkyd solution was mixed and heated to 60 °C until the deltamethrin was completely dissolved.
  • surfactant polyvinylalcohol with a molecular weight of 31000 g/mol and 88 mol% hydrolysis, commercial name Mowiol ® 4-88 (Sigma-Aldrich)
  • the emulsion was prepared at 60 °C by adding the alkyd solution into the aqueous solution and mixing at high speed (at least 4000 rpm, the higher the lower the final particle size) for 10 minutes using a high shear mixer (Silverson). After emulsification the solution was allowed to cool and the solvent (methyl ethyl ketone) was removed using a rotary evaporator. The removal of the solvent was confirmed gravimetrically: the quantity of solvent (methyl ethyl ketone) was known from the formulation (already present in the alkyd) and monitored during the removal of the solvent until the mass of the solution has decreased by the quantity of the solvent present.
  • the resulting emulsion was highly similar to the ones obtained with the indirect method.
  • the particle size distribution (d(0.5) varied between 2 (4%wt relating to the total quantity of emulsion surfactant) and 3 (6%wt surfactant) micron.
  • Particle size could be varied by changing parameters such as type of surfactants, mixing speed, process temperature or neutralization of the alkyd.
  • the particle size was measured using Mastersizer 2000, an instrument manufactured by Malvern.
  • the instrument uses laser diffraction to determine the particle size based on Mie Theory. In this technique the particle size is determine by analysing the scattering pattern of the particles.
  • the model number is MAL 1024504.
  • the software used was supplied by manufacturer and it was version 5.6. The measurement was done using standard operating procedures using a value of 1 .54 for the refractive index of alkyd.
  • a typical measurement involves the following steps: cleaning of the dispersing unit, filling with demineralized water, adding a quantity of dispersant (if needed), circulating the mixture through the measuring cell, measuring the background level, adding a quantity of alkyd until an obscuration of 2-10% is obtained, measuring the sample 3 consecutive times and calculating the average.
  • the cone test has been used to determine the bio efficacy of the prepared materials against mosquitoes.
  • the bio efficacy of the materials is usually expressed at % of mosquitoes knocked down and dead after expose to panels painted with biocide (in this case deltamethrin)-comprising paint. The test is described below.
  • an emulsion was prepared of all 8 alkyds as listed above.
  • the target particle size was set at 5 micron, and some variation in particle size is observed depending on the type of alkyd. No optimization of particle size had been done.
  • Deltamethrin - a pyrethroid type of insecticide - was used added as biocide at 0.5 and 1 .0 wt%.
  • the median particle size for the different emulsions is shown in Figure 1 .
  • Emulsion stability upon storage is an important property as it allows longer time between encapsulation and application of the encapsulated biocide, e.g. in paint formation.
  • An emulsion of alkyd number 3 was prepared using the direct method. After preparation i.e. after 0 days of storage) the average particle size d(0.5) was about 2.3 micron (between 2.0 and 2.5 micron). The emulsion was stored in a closed flask at room temperature and the average particle size d(0.5) was measured at 16, 24 and 84 days of storage. These measurements revealed that the average particle size d(0.5) was stable during storage as the average particle size d(0.5) remained between 2.0 and 2.5 micron.
  • the main purpose for encapsulation is to provide the active (biocide or insecticide such as deltamethrin) with protection against racemization and degradation. After preparation, samples were stored for three weeks at 54°C which is taken as indicative for three years of ageing at room temperature.
  • Samples were prepared by dosing alkyd-encapsulated deltamethrin to an active content level of 0.01 % weight into a white waterbased wall paint in the PVC range of 20 - 80 (commercial paint of AkzoNobel). The paint was adjusted to pH 8, 9 and 10 and the samples were incubated at 54 °C for three weeks. HPLC measurements were performed at 0, 4, 7, 10, 14, 17 and 21 days to determine deltamethrin stability using the method as described elsewhere herein. The results were compared with samples containing the standard drop in (deltamethrin as 25 g/L suspension concentrate by Bayer). The paint was adjusted to pH 8, 9 and 10 and the samples were incubated at 54 °C for three weeks.
  • the deltamethrin activity is less than 100 %. Acid value did not seem to impact on the performance of alkyds as encapsulation mediums and there was no significant difference between long oil alkyds and very long oil alkyds. Overall, very long oil alkyds performed better due to the fact that they are high solids alkyds with only 2 % weight solvent as compared to 35 % for long oil alkyds. A lower solvent content is desirable because it adds a lower VOC penalty and it simplifies the production method since an additional step of solvent removal is not needed. It also reduces the diffusion of deltamethrin out of the encapsulation which is thought to be mediated by solvent.
  • Biological efficacy of alkvd-encapsulated biocide [0091 ] Encapsulation of the deltamethnn in very long oil alkyds improved the stability against racemization especially at pH 8 and 9 as shown above. But for encapsulation to be useful the active, in this case deltamethrin, also needs to have a bioavailability and efficacy against mosquitoes similar or better than the standard drop-in (of a 25 g/L of deltamethrin suspension concentrate in paint). A significant lower efficacy against mosquitoes is indicative that the encapsulation is too efficient and it prevents the migration of deltamethrin to the surface of the paint.
  • Table 1 The particle size of the different emulsions based on alkyd number 6
  • the alkyd number 6 variants exhibited a wide variation of efficacy against the tested mosquitoes, ranging from poor for variant 6 (40 % of mosquitoes knocked down and dead after 48 hours) to similar to the standard drop-in for variant 2 (85 % of mosquitoes knocked down and dead after 6 hours.
  • the bio efficacy of deltamethrin encapsulated in a very long oil alkyd was tested in a similar way using the cone test method.
  • the encapsulated material was incorporated in a white waterbased wall paint in the PVC range of 20 - 80 using standard vinyl acetate as latex at 0.1 % weight active level.
  • the results from the test are presented in Figure 7 and they indicate similar levels of efficacy against the tested mosquitoes as the paint that only just received the drop-in.
  • the standard drop-in show a better efficacy for the initial period but the difference between the samples is very close to the experimental error of the measurement.
  • Samples were prepared using very long oil alkyds (numbers 4 and 5) in process similar to the one used for deltamethrin, namely direct emulsification.
  • the emulsification method resulted in a particle size distribution of the emulsions at the end of the process of 5 microns for alkyd number 4 and 10 microns for alkyd number 5. So, the emulsions with permethrin have similar mean particle size to the ones with deltamethrin.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Agronomy & Crop Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une émulsion d'un alkyde comprenant un biocide dans une solution aqueuse, la solution aqueuse comprenant entre 0,1 et 10 % en poids de tensioactif, un procédé destiné à préparer une telle émulsion et une composition de revêtement comprenant une telle émulsion.
PCT/EP2018/061018 2017-05-03 2018-04-30 Biocide encapsulé dans un alkyde WO2018202616A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18719913.8A EP3618631A1 (fr) 2017-05-03 2018-04-30 Biocide encapsulé dans un alkyde
BR112019021228A BR112019021228A2 (pt) 2017-05-03 2018-04-30 emulsão de um alquídico em uma solução aquosa, processo para pulsão, composição dreparação da eme revestimento, substrato revestido com um revestimento de uma composição de revestimento, processo de revestimento e uso de uma composição de revestimento
RU2019137971A RU2724547C1 (ru) 2017-05-03 2018-04-30 Капсулированный алкидом биоцид
CN201880024197.9A CN110545668A (zh) 2017-05-03 2018-04-30 醇酸包封的生物杀伤剂

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17169322.9 2017-05-03
EP17169322 2017-05-03

Publications (1)

Publication Number Publication Date
WO2018202616A1 true WO2018202616A1 (fr) 2018-11-08

Family

ID=58669674

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/061018 WO2018202616A1 (fr) 2017-05-03 2018-04-30 Biocide encapsulé dans un alkyde

Country Status (6)

Country Link
EP (1) EP3618631A1 (fr)
CN (1) CN110545668A (fr)
AR (1) AR111626A1 (fr)
BR (1) BR112019021228A2 (fr)
RU (1) RU2724547C1 (fr)
WO (1) WO2018202616A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4086313A1 (fr) * 2021-05-04 2022-11-09 Daw Se Substance de revêtement aqueuse, revêtement obtenu à partir de la substance de revêtement, ainsi que substrat contenant le revêtement

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2142239A (en) * 1983-06-27 1985-01-16 Shy Ying Wang Robert Insecticide paint
EP0198165A1 (fr) * 1985-04-13 1986-10-22 DESOWAG Materialschutz GmbH Produit de préservation du bois
EP0201214A2 (fr) 1985-04-10 1986-11-12 Nippon Paint Co., Ltd. Procédé de fabrication de microparticules de polymére ayant une activité pesticide
EP1112687A2 (fr) * 1999-12-27 2001-07-04 Chemkor Co., Ltd. Compositions insectifuges et peinture de répulsion contenant cette composition
US20040134377A1 (en) * 2002-12-30 2004-07-15 Lee Han Lim Paint composition
WO2006070183A1 (fr) 2004-12-30 2006-07-06 Syngenta Limited Compositions de revetement aqueuses
EP2489704A1 (fr) * 2009-10-15 2012-08-22 Maria Pilar Mateo Herrero Peintures insecticides et acaricides inhibitrices de la synthèse de chitine, régulatrices de l'hormone juvénile d'insectes et répulsives d'arthropodes, pour la lutte contre les maladies endémiques, les invasions et les allergènes
EP2545775A2 (fr) 2005-09-29 2013-01-16 Everris International B.V. Compositions agrochimiques à libération contrôlée granulaire et son procédé de préparation
WO2013064441A1 (fr) 2011-10-31 2013-05-10 Akzo Nobel Coatings International B.V. Peintures insecticides améliorées
EP2851401A1 (fr) 2013-07-23 2015-03-25 Mateo Herrero, Maria Pilar Composition biocide pour la lutte contre les nuisibles et les espèces envahissantes, produits de revêtement et leur utilisation

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1046267A1 (ru) * 1982-04-05 1983-10-07 Всесоюзный Научно-Исследовательский Институт Комплексных Проблем Полиграфии Краска дл офсетной или высокой печати
CN1169887C (zh) * 2001-10-24 2004-10-06 赵培基 环保杀虫乳胶漆及其生产工艺

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2142239A (en) * 1983-06-27 1985-01-16 Shy Ying Wang Robert Insecticide paint
EP0201214A2 (fr) 1985-04-10 1986-11-12 Nippon Paint Co., Ltd. Procédé de fabrication de microparticules de polymére ayant une activité pesticide
EP0198165A1 (fr) * 1985-04-13 1986-10-22 DESOWAG Materialschutz GmbH Produit de préservation du bois
EP1112687A2 (fr) * 1999-12-27 2001-07-04 Chemkor Co., Ltd. Compositions insectifuges et peinture de répulsion contenant cette composition
US20040134377A1 (en) * 2002-12-30 2004-07-15 Lee Han Lim Paint composition
WO2006070183A1 (fr) 2004-12-30 2006-07-06 Syngenta Limited Compositions de revetement aqueuses
EP2545775A2 (fr) 2005-09-29 2013-01-16 Everris International B.V. Compositions agrochimiques à libération contrôlée granulaire et son procédé de préparation
EP2489704A1 (fr) * 2009-10-15 2012-08-22 Maria Pilar Mateo Herrero Peintures insecticides et acaricides inhibitrices de la synthèse de chitine, régulatrices de l'hormone juvénile d'insectes et répulsives d'arthropodes, pour la lutte contre les maladies endémiques, les invasions et les allergènes
WO2013064441A1 (fr) 2011-10-31 2013-05-10 Akzo Nobel Coatings International B.V. Peintures insecticides améliorées
EP2851401A1 (fr) 2013-07-23 2015-03-25 Mateo Herrero, Maria Pilar Composition biocide pour la lutte contre les nuisibles et les espèces envahissantes, produits de revêtement et leur utilisation

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Coatings Technology Handbook", pages: 435 - 437
A. NAVAS DIAZ ET AL., JOURNAL OF CHROMATOGRAPHIC SCIENCE, vol. 36, 1998, pages 210 - 216
ACHARYA B N ET AL: "Effects of the process of the incorporation of deltamethrin on slow release property of insecticidal paint", PIGMENT AND RESIN TECHNOLOGY,, vol. 33, no. 1, 1 January 2004 (2004-01-01), pages 21 - 25, XP009194946, ISSN: 0369-9420 *
ANONYMOUS: "Commercial development of a household insecticidal emulsion paint", 15 December 2011 (2011-12-15), XP055392079, Retrieved from the Internet <URL:http://www.imr.gov.my/index.php/en/research-a-publication/commercialised-product/34-commercial-development-of-a-household-insecticidal-emulsion-paint?presets=red> [retrieved on 20170719] *
KARIN L. SCHIØLER ET AL: "Insecticidal Paints: A Realistic Approach to Vector Control?", PLOS NEGLECTED TROPICAL DISEASES, vol. 10, no. 4, 21 April 2016 (2016-04-21), pages e0004518, XP055391293, DOI: 10.1371/journal.pntd.0004518 *
R. JAMES MAGUIRE, J. AGRIC. FOOD CHEM., vol. 38, 1990, pages 1613 - 1617

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4086313A1 (fr) * 2021-05-04 2022-11-09 Daw Se Substance de revêtement aqueuse, revêtement obtenu à partir de la substance de revêtement, ainsi que substrat contenant le revêtement

Also Published As

Publication number Publication date
CN110545668A (zh) 2019-12-06
BR112019021228A2 (pt) 2020-04-28
RU2724547C1 (ru) 2020-06-23
EP3618631A1 (fr) 2020-03-11
AR111626A1 (es) 2019-07-31

Similar Documents

Publication Publication Date Title
DE69821940T2 (de) Landwirtschaftlich aktive inhaltsstoffe enthaltende mikropartikel
AU2008267383C1 (en) A method for modulating the release rate of microencapsulated active ingredients
JP2005528200A (ja) ポリウレアカプセル中に疎水性有機分子をカプセル化する方法
US20110274763A1 (en) Slow releasing microcapsules and microspheres containing an active substance
EP2387308B1 (fr) Procédé de préparation des particules pour libération contrôlée d&#39;un biocide
JP2013513663A (ja) 徐放性シリカマイクロカプセル
DE1935873A1 (de) Filme,die langsam einen verfluechtigbaren Stoff abgeben,und Verfahren zu ihrer Herstellung
US20140294968A1 (en) Polyacrylate-based active compound-comprising particles
AU2008346511A1 (en) A method for modulating the release rate of microencapsulated actives
KR100348436B1 (ko) 방충 조성물 및 이를 사용한 방충 도료
WO2018202616A1 (fr) Biocide encapsulé dans un alkyde
Acharya et al. Deltamethrin microencapsulation in emulsion paint binder and its long-term efficacy against dengue vector Aedes aegypti
US20120015017A1 (en) Slow releasing microcapsules containing an active substance
IL109118A (en) Multiply-coated particles
Boh Microencapsulation and testing of the agricultural animal repellent, Daphne
EP3654926B1 (fr) Parfums encapsulés dans un polymère à libération régulée
EP0877650B1 (fr) Microparticules contenant une substance active et un materiau polymere formant la paroi d&#39;une capsule, leur procede de fabrication et leur utilisation
KR0168428B1 (ko) 수현탁형 피레스로이드계 살충 조성물 및 이를 사용한 논 해충의 방제방법
KR950006942B1 (ko) 고형수성 방충도료 조성물
JP6955353B2 (ja) 水性塗料組成物
DE102019119888A1 (de) Neue Formulierung auf Basis eines Oleogels insbesondere zur Freisetzung von volatilen Komponenten und Verfahren zu dessen Herstellung
WO2015145393A2 (fr) Microencapsulation de classes de composés de type perméthrine ou pyréthroïdes pour une application dans les cosmétiques, les textiles industriels et techniques, et les revêtements de surface
JP2018104606A (ja) 塗料組成物、塗膜および物品
WO2003077651A1 (fr) Formulation de microparticules a toxicite aquatique reduite
CN103857753B (zh) 杀虫漆

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18719913

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112019021228

Country of ref document: BR

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018719913

Country of ref document: EP

Effective date: 20191203

ENP Entry into the national phase

Ref document number: 112019021228

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20191009