BR112019021228A2 - emulsion of an alkyd in an aqueous solution, pulsation process, eme-coating composition, substrate coated with a coating composition coating, coating process and use of a coating composition - Google Patents

Abstract

the present invention relates to an alkyd emulsion comprising biocide in an aqueous solution wherein the aqueous solution comprises between 0.1 and 10% by weight of surfactant, a process for preparing such an emulsion and for a coating composition comprising such an emulsion .

Description

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EMULSION OF AN ALQUIDIC IN A WATER SOLUTION, PROCESS FOR PREPARING THE EMULSION, COATING COMPOSITION, COATED SUBSTRATE WITH A COATING OF A COATING COMPOSITION, COATING PROCESS AND USE OF A COATING COMPOSITION

FIELD OF THE INVENTION [001] The present invention relates to an emulsion of an alkyd in an aqueous solution, wherein the alkyd comprises an optically active biocide, a process for preparing emulsion and a coating composition comprising such an emulsion.

HISTORY OF THE INVENTION [002] 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 inks are solvent-borne, that is, most, if not all, of the carrier liquid is organic solvent. This is mainly because insecticides are large organic molecules that do not readily dissolve in aqueous paints, particularly with a low level of VOC (volatile organic content) required by legislation and consumers worldwide.

[003] Paints, comprising an insecticide (ie, an insecticidal paint) can be made by adding the desired amount of insecticide to the final paint composition.

[004] Ready-to-use insecticidal paints are known. Such inks are disclosed in document WQ2006 / 070183 and comprise an insecticide encapsulated by thin layers of cross-linked polymer. The capsules are formed

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2/36 of highly cross-linked polyurea or cross-linked aminoplastic resins and require complex and expensive production processes. Such cross-linked polymers do not form films at room temperatures.

[005] In WO201364441 it is revealed that certain insecticides remain active in the dry paint film for only a short time, sometimes only a few days, resulting in dry paint films that do not contain active insecticide, or at least so little that it is less than the minimum effective amount needed to kill all or some of the insects. Insecticides that are likely to dry the film in this way are volatile. Typically, interior architectural paint is expected to last many months and possibly a year or more. Of course, consumers expect that the insecticidal activity of an insecticidal paint will also last for a similar period of time. A way to make low-VOC aqueous insecticidal architectural paints, comprising volatile insecticides is disclosed in WO201364441. It reveals a simple method without the need to encapsulate the insecticide in the crosslinked polymer.

[006] Various encapsulation methods are known in the art, for example, matrix encapsulation, in which the active compound is dispersed in the encapsulation material (beads, microparticles, microspheres); or core / shell encapsulation, where the active compound is confined as a core by one shell or more (multiple shell) Core / shell encapsulation is also sometimes 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

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3/36 filling, while the wall is sometimes called a shell, coating or membrane.

[007] EP2851401 discloses a biocidal composition to control invasive species and pests, their coating products and their use. It reveals the microencapsulation of the active substances with a binder in a polymer and mineral coating. Microencapsulation of the active substance, for example, insecticide, is achieved using polymerization of a binder in a polymeric or mineral coating creating a core-shell structure around the active substance. Encapsulation requires the polymerization of at least one monomer in the interphase of two immiscible substances, giving rise to a membrane that constitutes the microcapsule wall (core / shell encapsulation).

[008] In matrix encapsulation, the active ingredient is dispersed evenly throughout the continuous material (matrix) and the main release profile is extended release where the active is released slowly over time For this type of encapsulation to be effective , several conditions need to be met. First, the asset must have a very high partition coefficient (solubility) in the material. Second, the matrix of choice needs to be insoluble in water, as well as active, and inert to other components of the formulation. The matrix must have a high glass transition temperature or reasonable crosslinking to allow a slow diffusion of the asset outside the matrix.

[009] EP201214 discloses polymeric microparticles that have a pesticide attached to them in which the active substances are attached to the outer surface of the microparticles.

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4/36 [010] Also, combinations of encapsulation techniques are known, such as, for example, from EP2545775 which discloses a granular core material with a first layer of wax coating comprising a biologically active ingredient incorporated there and a second coating layer including a polymeric composition.

[011] Inesfly ® products use microencapsulation technology, which is the key element that gives Inesfly products their special characteristics. The formation of Inesfly Technology is a chemical process that produces microcapsules in suspension. These microcapsules are a kind of core-shell through which there is a core that comprises the asset and a shell, wall or structure that surrounds the former, without the asset. These microcapsules include conventional biocides at very low and regular doses of insect growth. The gradual and controlled release of microencapsulated active ingredients is a direct result of the polymeric coverage (www. Inesf lyaf rica .. com).

[012] The product known as Painticide, released in collaboration with the Institute for Medical Research (IMR), is an emulsion paint formulation impregnated with a pyrethroid (deltamethrin) that allows the insecticide to slowly release on the wall surface (http: // ww. imr. gov.my/). It reveals a drop of deltamethrin in the ink formulation after which the biocide is trapped in the resulting ink formulation.

[013] Many insecticides, including many in the pyrethrin class, comprise one or more chiral centers and the insecticidal activity of the insecticide often differs

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5/36 between different enantiomers, diastereomers or epimers. A problem with the existing coating and / or paint compositions that comprise insecticides is that due to alkaline conditions such as fresh paint, racemization of one or more of the chiral centers can occur in the fresh paint reducing the effective active insecticide concentration. This is especially the case with water-based coating compositions. To maintain a minimum level of active concentration of the insecticide, a doubling of the concentration of insecticide is required for each chiral atom, where racemization can occur during storage. This would increase the costs of the coating composition and can also influence the quality of the coating. In addition, there is a trend towards a reduction in authorized active substances or a reduction in levels of authorized active substances.

[014] Thus, there is a need in the art for a water-based coating composition comprising an insecticide in which a chiral insecticide does not racemize.

SUMMARY OF THE INVENTION [015] It has now been discovered that racemization of an insecticide in a water-based paint (i.e., coating composition) can be reduced by using an insecticide matrix-type encapsulation in an alkyd that reduces racemization of an optically active insecticide. The encapsulated alkyd insecticide can be added to a coating composition and still maintain its protective environment for the insecticide in the coating composition. Alkyd encapsulation prevents the racemization insecticide or at least slows the racemization. Furthermore, the alkyd encapsulation does not prevent the migration of the insecticide to the

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6/36 surface of the coating layer (dry) and therefore allows prolonged insecticide activity. It is understood that this type of alkyd encapsulation can also be applied more generally to optically active biocides.

[016] Consequently, the present invention provides an emulsion of an alkyd in an aqueous solution in which the alkyd comprises an optically active biocide and the aqueous solution comprises between 0.1 and 10% by weight of surfactant, in which the amount of solvent non-aqueous is less than 15% by weight, and where the pH of the emulsion is between 7 and 11.

[017] The invention further provides a process for preparing such an emulsion and a coating composition comprising such an emulsion.

DEFINITIONS [018] The term alkyd here refers to polyester derived from polyols such as pentaerythritol, propenoglycol trimethylolpropane and a dicarboxylic acid such as phthalic acid or maleic acid or carboxylic anhydride such as phthalic acid anhydride or maleic acid anhydride. Alkyds can also comprise triglycerides derived from polyunsaturated fatty acids (often derived from plant and vegetable oils, for example, flaxseed 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 polyester containing fatty acid. Alkyds can be used in paints or coating compositions. The different levels of oil in the ink provide different ink characteristics. Alkyds and alkyd-based paints can be diluted with solvents to allow

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7/36 easier handling. Other important components of alkyd paint are pigments and extenders. The pigment is the substance that gives the color of the paint. 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 mass of paint. Extenders are also used to adjust the consistency of the paint and to lower colored pigments of great pretending strength. The last major category of alkyd paint components comprises additives, for example, to accelerate the drying of paint.

[019] Alkyds can be classified based on a wide range of properties such as oil length and acid value, see for example Coatings Technology Handbook, Second Edition edited by D. Satas, Arthur A. Tracton pages 435 to 437, which is included here by reference.

[020] Oil length is defined as% by weight of the 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 more; long oil: between 60 and 75%; medium oil: between 45 and 60%; short oil: up to 45%.

[021] 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 (IUPAC definition). It is determined using a standard solution of potassium hydroxide (0.1 N) in methanol and one percent phenolphthalein in ethanol (95 percent) as an indicator. A mixture of ethanol — toluene is prepared by mixing equal volumes of ethanol (95 percent) and toluene and neutralized with a methanolic solution of hydroxide

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8/36 potassium (0.1 N) in the presence of phenolphthalein as an indicator. 1 to 2 g of the sample are dissolved in 50 ml of the ethanol-toluene mixture. The solution is titrated with methanolic solution of potassium hydroxide in the presence of phenolphthalein as an indicator. The acid value is calculated as follows:

[022] Acid value = 56.1 an / p.

[023] Where a = mL methanolic solution of potassium hydroxide [024] N = normality of methanolic solution of potassium hydroxide [025] p = weight of the sample in g (see recommended methods for the analysis of alkyd resins by IUPAC: https://www.iugac.org/ under subpage publications / pac2007 / 1973 / pdf / 3302x0411.pdf.) [026] Enantiomer ratio is defined as the quantity of the first enantiomer (El) divided by the quantity of the second enantiomer (E2 ), that is, E1 / E2.

[027] Enantiomer fraction is defined as the quantity of the first enantiomer divided by the total quantity of the first and the second enantiomer, that is, El / (El + E2).

[028] Excess enantiomer is defined as the absolute value of the difference in the quantity of the first enantiomer and second enantiomer, that is, | E1 - E2 | where El + E2 = 1 (or 100%).

[029] Surfactant refers to compounds that decrease surface tension (or interfacial tension) between two liquid surfactants that can act as detergents, wetting agents, emulsifiers, foaming agents and dispersants. Surfactants are usually

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9/36 organic compounds that are amphiphilic, meaning that 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. The surfactants will diffuse in water and absorb at the 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 outside the bulk aqueous phase, in the air or in the oil phase, while the water-soluble head group remains in the aqueous phase. Most commonly, surfactants are classified according to the polar head group. A non-ionic surfactant has no groups loaded on its head. The head of an ionic surfactant carries a positive or negative net 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 called zwitterionic. Anionic surfactants contain anionic functional groups in their heads, such as sulfate, sulfonate, phosphate and carboxylate and are well known in the art. Nonionic surfactants include many long-chain alcohols that exhibit some surfactant properties, for example, fatty alcohols, cetyl alcohol (hexadecan-1-ol or palmityl alcohol), stearyl alcohol and oleyl alcohol. Other examples of non-ionic surfactants include polyethylene glycol alkyl ethers (eg octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether), polypropylene glycol alkyl ethers, glycoside alkyl ethers (eg glycoside decyl, lauryl glycols glycoside), ethers

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10/36 polyethylene glycol octylphenols (eg, triton X100), polyethylene glycol alkylphenols (eg, nonoxynol-9), glycerol alkyl esters (eg, glyceryl laurate), polyoxyethylene glycol sorbitan alkyl esters (by example, polysorbate), allyl esters of sorbitan, cocamide MEA, cocamide DEA, dodecyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, polyethoxylated tallow amine (POEA) or mixtures thereof.

[030] Average particle size d (0.5) of the emulsion refers to the median diameter or the average value of the particle size distribution in the emulsion. It is the value of the particle diameter at 50% in the cumulative distribution. For example, if D (0.5) = 9.1 pm, then 50% of the particles in the sample are greater than 9, 1 pm, and 50% less than 9, 1 pm. The average particle size can, for example, be measured using a Mastersizer 2000 instrument as described here elsewhere.

[031] A water-based coating or water-based paint composition is defined herein as a coating / paint composition in which the amount of non-aqueous solvent is less than 15% by weight, preferably less than 10% by weight. weight, more preferably less than 5% by weight, such as less than 4, 3, 2, or even less than 1% by weight.

[032] A coating composition can be applied to the surface of an object, commonly referred to as the substrate. The purpose of applying the coating can be decorative, functional or both. The coating itself can be a coating on all sides, completely covering the substrate, or it can cover only parts of the substrate.

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Paints and lacquers are coatings that most often have dual use of substrate protection and are decorative, although some paints by artists are for decoration only, and the paint in large industrial pipes is presumably only for the function of preventing corrosion. After applying the coating composition to a substrate, the coating composition dries / cures to become a dry coating film or substrate coating. Drying and curing of a coating occurs, for example, by the evaporation of solvents and polymerization reactions between different components in the coating composition.

[033] Percentages by weight (% by weight) of an ingredient in a composition are expressed as the percentage by weight of the specific ingredient compared to the weight of the total composition.

FIGURES [034] Figure 1 - average particle size d (0.5) of emulsions prepared from eight (8) different alkyds as listed in the examples containing deltamethrin in 0.5 and 1.0% by weight (black column and gray, respectively).

[035] Figure 2 - active isomer of deltamethrin (%), (as a stability measurement for racemization) in a water-based (water-based) coating composition is shown when added as a standard white ink drop-in of water-based wall in the PVC range from 20 to 80 as a function of pH.

[036] Figure 3 - Deltamethrin stability when encapsulated in a very long oily alkyd emulsion as compared to the standard drop-in (DMN-SC) as a function of

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12/36 pH. Figure 3A for pH = 8, Figure 3B for pH = 9 and Figure 3C for pH = 10.

[037] Figure 4 - stability of deltamethrin when encapsulated in long oily alkyl emulsion as compared to the standard drop-ín (DMN-SC) as a function of pH. Figure 4A for pH = 8, Figure 4B for pH = 9 and Figure 4C for pH = 10.

[038] Figure 5 - Deltamethrin stability when encapsulated in short and medium oily alkyd emulsion as compared to the standard drop-ín (DMN-SC) as a function of pH. Figure 5A for pH = 8, Figure 5B for pH = 9 and Figure 5C for pH = 1 [039] Figure 6 - Bioeffectiveness for eight deltamethrin encapsulation variants in alkyd number 6 compared to the standard drop-in.

[040] Figure 7 - Bio-efficacy of deltamethrin encapsulated in alkyd of very long oil chain compared to the freshly prepared decrease of 0.1% in active weight in a water-based wall paint in the range of 20 to 80 PVC.

DETAILED DESCRIPTION OF THE INVENTION [041] The invention relates to an emulsion of an alkyd in an aqueous solution characterized by the fact that the alkyd comprises an optically active biocide and the aqueous solution comprises between 0.1 and 10% by weight 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 to drop into the compositions.

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13/36 [042] The length of alkyd oil may vary in the emulsion of the invention. In one aspect, the length of alkyd oil is greater than 60%, preferably where the length of alkyd oil is greater than 75%. Also, mixtures of alkyds with different lengths of oil can be used.

[043] 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 yet 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.

[044] The emulsion obtained according to the invention can comprise different amounts of surfactant concentration and / or type of surfactant. In one aspect of the invention, the surfactant is selected from one or more members of the group consisting of nonionic surfactants and ionic surfactants; preferably, the surfactant is a non-ionic surfactant. In one embodiment, the non-ionic surfactant is polyvinyl alcohol of average levels of hydrolysis (eg 88%) and average molecular weight (eg 31000 Da). Also, the amount of surfactant can be varied to drive the characteristics of the emulsion. In one aspect, the concentration of surfactant in the emulsion obtained in the method according to the invention to encapsulate a biocide in an alkyd is between 0.1 and 10% by weight, or in another embodiment between 1 and 9% by weight or between 2 and 8% by weight, or even between 3 and 7% by weight. In another embodiment the amount of non-ionic surfactant in the emulsion obtained in the method according to the invention to encapsulate a biocide in an alkyd is between 0.1 and 10% by weight, or in another

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14/36 between 1 and 9% by weight or between 2 and 8% by weight, or between 3 and 7% by weight.

[045] Also, the amount of non-volatiles can vary in the emulsion of the invention. In one aspect, the emulsion of an alkyd in an aqueous solution of the present invention comprises between 20 and 60% non-volatiles, preferably between 35 and 50% non-volatiles. In another embodiment, it is between 30 and 55% by weight. In yet another embodiment it is between 40 and 50% by weight. In yet another embodiment, it is between 38 and 42% by weight.

[046] A problem with the existing coating and / or paint compositions comprising insecticides is that due to alkaline conditions such as in fresh paint, racemization of one or more of the chiral centers can occur in fresh paint by reducing the effective active concentration of the insecticide . As illustrated in the examples, encapsulation of a biocide in an emulsified alkyd 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, for example insecticides such as deltamethrin, is known to occur under basic conditions. Under neutral conditions, the rate of racemization is generally lower than under basic conditions. Therefore, the invention relates to an emulsion of an alkyd in an aqueous solution as described here, where the pH of the emulsion is between 7 and 11, preferably between 8 and 10, or where the pH of the emulsion is between 8 and 9. In yet another realization, it is between 7.5 and 10.5. Also, the pH of a coating composition comprising an emulsion of an alkyd in an aqueous solution as described here, is in an aspect between 7 and 11, in

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15/36 another realization between 7.5 and 10.5, or even between 8 and 10, in yet another realization is between 8 and 9.

[047] The amount of biocide in an alkyd emulsion in an aqueous solution according to the current invention depends on the type of biocide used. It is understood that biocides can have different minimum concentrations in order to be effective. In another aspect, the invention relates to an emulsion of an alkyd in an aqueous solution of the current invention, in which the amount of biocide in the emulsion is less than 10% by weight, for example, less than 9, 8, 7, 6 , 5, 4, 3% by weight or even less than 2% by weight or less than 1% by weight. In another aspect, it is between 0.001 and 10% by weight calculated from the weight of the emulsion. In yet another aspect, it is between 0.001 and 6% by weight, or between 0.01 and 6% by weight, for example, between 0.01 and 5% by weight, between 0.1 and 6% by weight, or even in another embodiment between 1 and 6% by weight, or in yet another embodiment between 0.01 and 2% by weight, or even between 0.1 and 1% by weight. In one embodiment it is between 2 and 5% by weight.

[048] 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 can be stored at room temperature. The average particle size d (0.5) of the emulsion does not affect the stability of the biocide, so in one aspect, there is no restriction on the average particle size d (0.5) of the emulsion. In one aspect, the average particle size d (0.5) of the emulsion is below 1.0 microns. In another aspect, the average particle size d (0.5) of the emulsion is between 0.5 and 30 microns or in another aspect between 1 and 11 microns. In yet another aspect, the average particle size

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16/36 d (Ο, 5) of the emulsion is between 5 and 10 microns. In an additional aspect, the average particle size d (0.5) of the emulsion remains stable during storage. It is understood that the larger particles in an emulsion can resolve during storage, they can be redispersed using methods known in the art, such as using low shear mixture.

[049] In another aspect, the invention relates to an emulsion of an alkyd in an aqueous solution of the current invention in which the optically active biocide is an optically active insecticide. In one embodiment, the insecticide is a pyrethroid or pyrethrin. The class of insecticides called pyrethroids comprises insecticides such as Alethrin, Bifenthrin, Cyphlutrin, Cypermethrin, Cyphenothrin, Deltamethrin, Sphenolvalerate, Etofenprox, Fenpropatrin, Fenvalerate, Flucitrinate, Flumethrin, Imiprothrine, Setrofletrine, Permethrin, LambdaCialotalin, LambdaCialotalin tau-Fluvalinate, Teflutrina, Tetrametrina, Tralometrina and Transflutrina.

[050] Preferably, the optically active 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 a chiral center that is known to racemize under alkaline conditions. Deltamethrin has a rapid action against invasive species, a short period of relative contact between species and deltamethrin is sufficient to be effective, for example, an insect that lands on a substrate coated with a

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The coating composition according to the invention can be long enough for deltamethrin to be effective against the insect.

[051] In yet another aspect, 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:

i. providing an aqueous solution of a surfactant comprising between 0.1 and 10% by weight of the surfactant, ii. providing an alkyd optionally dissolved in a solvent iii. providing an optically active biocide, iv. dissolution of the biocide in the alkyd,

v. emulsification of the biocide dissolved in the alkyd of step iv in the aqueous solution of step I, vi. adjustment of the emulsion pH to a value between 7 and 11, preferably between 8 and 10, or to a value between 8 and 9.

[052] It is understood that steps ii, iii and iv can be replaced by an alternative step of supplying a biocide dissolved in an alkyd. This is particularly interesting when the desired biocide solution in the desired alkyd can be obtained. In one embodiment, the invention relates to the process as described above comprising the alternative step instead of steps ii, iii and iv. In another aspect, the invention refers to a

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18/36 an alkyd emulsion in an aqueous solution obtained in this process.

[053] The emulsification of an alkyd in an aqueous solution can be done by adding the aqueous solution in the alkyd, or by adding the alkyd in the aqueous solution. In one embodiment of the process for preparing the emulsion according to the current invention, in step v, the emulsion is prepared by adding the aqueous solution in the alkyd, or by adding the alkyd in the aqueous solution; preferably by adding the alkyd in the aqueous solution as its method of preparation allows a wider range of emulsion properties to be achieved (for example, particle size). The variation of process parameters, such as mixing time, mixing speed, rate of addition, ratio between surfactants used, process temperature, can influence the characteristics of the emulsion obtained.

[054] Based on simple modeling using Fick's diffusion laws, it is assumed that the rate of leaching of the asset (for example, biocide or insecticide) outside the alkyd encapsulation is controlled by the type of matrix (ie, type alkyd) and particle size (controlled by process parameters). In order to decrease the amount of leachate active, a larger particle size is desirable, although this could also impact on the storage stability of the emulsion. A decrease in the diffusion coefficient that can be influenced by the type of alkyd, also leads to a decrease in the amount of leachate active.

[055] The emulsion of the present invention can be added to the coating composition. Was

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19/36 surprisingly discovered that the reduced racemization of the biocide, as found in the emulsion of an alkyd in an aqueous solution characterized by the fact that the alkyd comprises a biocide, is maintained when such an emulsion is added to a coating composition. Thus, in a further aspect, the invention relates to a coating composition which comprises the emulsion of an alkyd in an aqueous solution characterized by the fact that the alkyd comprises a biocide as defined herein. 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. In another embodiment, in such a coating composition, the relative amount of active enantiomer of the biocide after 3 weeks of storage at 54 ° C is at least 2% greater 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. In a further aspect, the amount of biocide in such a coating composition is between 0.0001 and 5% by weight, or the amount of insecticide in such a coating composition is between 0.0001 and 5% by weight.

[056] In yet another aspect, the invention relates to a coating composition comprising the emulsion of an alkyd in an aqueous solution characterized by the fact that the alkyd comprises a biocide as defined herein, wherein the pH of the coating composition it is between 7 and 11, preferably between 8 and 10, or where the pH of the coating composition is between 8 and 9. The coating composition can be a latex or other type of paint. And the

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20/36 water based. In another aspect, the racemization of the biocide in the coating composition comprising the emulsion of an alkyd in an aqueous solution characterized by the fact that the alkyd comprises a biocide according to the invention, is less than 50% when stored at 54 ° C for 3 weeks. In other words, after 3 weeks of storage at 54 ° C, more than 50% of the biocide has the same configuration (it is the same enantiomer / stereoisomer) as at the beginning of the storage period. In another embodiment, the racemization of the biocide is less than 45%, for example, less than 40%, 35%, 30%, 25%, 20%, 15%, 10% or even less than 5% when stored at 54 ° C for 3 weeks.

[057] In yet another aspect, the excess of active enantiomer enantiomer of the biocide in a coating composition comprising the alkyl encapsulated biocide according to the invention, after 3 weeks of storage at 54 ° C, is at least 2% greater , for example, at least 3%, 4%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80% or even at least 90% greater than the excess enantiomer of the active enantiomer in an identical coating composition comprising the same amount of biocide via drop in. In other words, starting with two containers comprising the same coating composition, the biocide (with an excess of known enantiomer) is added to the first in the form of an alkyl encapsulated biocide as described here, the same amount of biocide with the same excess of enantiomer is added to the second container via drop in. Thus, the amount of biocide (% by weight) in the two containers is the same. The two containers are stored under the same conditions (closed container,

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21/36 mixing the alkyd through the coating composition, storage at 54 ° C for 3 weeks).

[058] It is understood that drop in of a biocide in a coating composition means that the biocide is added to the coating composition in pure form, that is, the pure biocide (or a solution of it) is added in drops to the composition of coating to the desired concentration.

[059] Depending on the biocide, final concentrations other than the biocide in the coating composition may be desirable. Thus, in another aspect of the invention, the relative amount of biocide in a coating composition comprising an alkyd encapsulated biocide according to the invention is between 0.001 and 10% by weight of the coating composition. In another embodiment it is between 0.01 and 5% by weight of the coating composition. In one embodiment it is between 0.01 and 3% by weight. In yet another embodiment it is between 0.01 and 2.5% by weight. In yet another embodiment it is between 0.05 and 5% by weight or between 0.1 and 5% by weight. In yet another aspect of the invention, the relative amount of insecticide in a coating composition comprising the encapsulated alkyd insecticide according to the invention is between 0.001 and 5% by weight of the coating composition. In one embodiment it is between 0.01 and 3% by weight. In yet another embodiment it is between 0.01 and 2.5% by weight. In yet another embodiment it is between 0.05 and 2.5% by weight. Preferably, the amount of biocide is less than 2.5% by weight, for example 2.0, 1.5 or 1.0% by weight. Consequently, in one embodiment, the amount of biocide in the coating composition of the invention is between 0.001 and 1.0% by weight. In another embodiment, the amount of insecticide in the coating composition of the

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The invention is between 0.001 and 1.0% by weight. In yet another embodiment, the amount of deltamethrin in the coating composition of the invention is between 0.001 and 1.0% by weight. In a further aspect, the amount of biocide in the coating composition of the invention is between 0.0001 and 0.1% by weight.

[060] In yet another aspect of the invention, the relative amount of biocide in the emulsion of an alkyd in an aqueous solution in which the alkyd comprises a biocide according to the invention is less than 10% by weight, or in another embodiment less than 5% by weight. In another aspect it is between 0.01 and 10% by weight of the emulsion. In one embodiment it is between 0.01 and 5% by weight. In yet another embodiment it is between 0.01 and 2.5% by weight. In yet another embodiment it is between 0.05 and 5% by weight or between 0.1% by weight and 5% by weight or even between 0.1 and 2.5% by weight.

[061] In yet another aspect of the invention, the relative amount of insecticide in such an emulsion according to the invention is less than 10% by weight, or in another embodiment less than 5% by weight. In another aspect it is between 0.01 and 10% by weight of the emulsion. In one embodiment it is between 0.01 and 5% by weight. In yet another embodiment it is between 0.01 and 2.5% by weight. In yet another embodiment it is between 0.05 and 5% by weight or between 0.1% by weight and 5% by weight or even between 0.1 and 2.5% by weight.

[062] The emulsion according to the invention can be added to a coating composition to obtain a coating composition with biocidal activity. It can also be used to provide biocidal activity to other objects, or alternatively, the coating composition comprising the alkyd encapsulated biocide can be applied to products such as mosquito nets, clothing, nets

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23/36 insect repellents to cover open windows or doors or any other object that someone would like to have biocidal activity. Thus, in yet another aspect, the invention relates to an object comprising or immersed in or covered with the alkyd encapsulated biocide (e.g., insecticide) obtainable / obtained with the method of the invention. In one embodiment, the biocide is an insecticide, in yet another embodiment, the insecticide is deltamethrin.

[063] In yet another aspect, the invention relates to a container comprising the emulsion of an alkyd comprising a biocide in an aqueous solution according to the invention, or in another embodiment to a container comprising a coating comprising said emulsion . In one embodiment, the optically active biocide is an optically active insecticide, in yet another embodiment, the insecticide is deltamethrin.

[064] It is understood that the substrates can be coated with a coating composition comprising the emulsion of an alkyd in an aqueous solution characterized by the fact that the alkyd comprises a biocide as defined herein, using methods known in the art such as spraying, application by brush or roller, immersion of the substrate in the paint, etc. The substrates can be completely covered or partially covered. After drying the coating, the substrate is covered or partially covered by a dry coating film that has biocidal activity, for example, insecticidal activity, so that when insects touch the covered part of such substrate, they undergo the insecticidal activity of the insecticide present in the coating. Thus, in yet another aspect, the invention refers to a

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24/36 substrate or part thereof, coated with such a coating composition. After curing / drying such a coating layer, the dried coating layer slowly releases the biocide. Likewise, the invention also relates to a coating process which comprises the step of coating a substrate with a coating composition comprising the emulsion of an alkyd in an aqueous solution characterized by the fact that the alkyd comprises a biocide as defined herein. . The substrates obtained in such a process are also part of the invention.

[065] In one aspect, 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 for a substrate coated with emulsion deposited from the emulsion according to the invention.

[066] In a further aspect, the invention relates to the use of a coating composition according to the invention, a varnish, lacquer, paint, coating, stain, enamel, printing ink or floor covering, preferably in a varnish, lacquer, paint or coating.

[067] The invention is illustrated by means of the following non-limiting examples.

EXAMPLES [068] Eight (8) different alkyd resins were used for encapsulation. The characteristics of these alkyds are given below.

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Alkyd Number 1 2 3 4 Type Polyester Polyester Polyester Polyester unsaturated unsaturated unsaturated unsaturated in modified long oil long oil asolid urethane oil base base long elevated of Oil of soy of soy the base in Soy tall oil fatty acid in Length 63.0% 66.7% 61.3% 84, 1% of Oil Oil Soy Soy Soy TOFA

Polyol PentaerythritolPentaerythritolPentaerythritolPentaerythritol

Solids

57.0 to 59.0% 74.0 to 76.0% 64.0 to 66.0%

98.5 to 100%

Acid value <2 to 10 9 to 11 6 to 10

Solvent

Espirito Espirito Espirito white xylene / white xylene / white xylene / xylene

Alkyd Number 5 6 7 8 Type Long high unsaturated polyester based on tall oil fatty acid A polyester resin Oil InstalledUtilane short oil based tall oil urethane Oil length 85.7% 55.0% 40, 0% 59, 0% Oil TOFA TOFA Soy Polyol Pentaerythritol Pentaerythritol Pentaerythritol Solids 98.5 to 100% 85% 99 to 100% 50, 0 to 53.0% Acid value <10 9, 5 <11.5 13 to 17 Solvent Xylene MEK AT Xylene

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26/36 [069] Different packaging methods were used to test their impact on product stability:

INDIRECT EMULSIFICATION METHOD [070] A mixture of surfactants [nonionic (Maxemul 7101 - formerly Atlas G5000 [a nonionic surfactant sold by Croda Coatings & Polymers]): anionic surfactants (Empimin OT75 [a dialkyl sulfosuccinate by Huntsman]), 55: 45% w / w ratio] were used. Also, the best results were achieved when the alkyd was neutralized to 75% of the acid value using sodium hydroxide (ie, sufficient sodium hydroxide was added to decrease the acid value by 75% of the initial value) [071] jacketed stainless steel, preheated to 65 ° C, was loaded with alkyd, surfactant, biocide (deltamethrin) and antifoam and stirred for 5 minutes at 500 rpm using a suspended stirrer and a blade at a similar temperature. After 5 minutes, a 1 M aqueous solution of NaOH was added dropwise over 5 minutes, while increasing the mixing speed to 2000 rpm. After addition, the mixture was allowed to continue for another 30 minutes. At the end of the mixing, the emulsion was transferred to a storage vessel and allowed to cool to room temperature.

[072] The indirect method was tried on two different alkyds: numbers 3 and 2. The particle size distribution was similar in both cases (d (0.5) was about 4.3 microns). The size of the emulsion varied little over time and 10 to 15 minutes of mixing time was enough to achieve the desired particle size.

DIRECT EMULSIFICATION METHOD

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27/36 [073] The encapsulation method using direct emulsification consisted of the following steps. First, a solution of 5% by weight of surfactant (polyvinyl alcohol with a molecular weight of 31000 g / mol and 88% by mol of hydrolysis, trade name Mowiol ® 4-88 (Sigma-Aldrich)) in water was prepared and heated at 60 ° C. Separately, deltamethrin (100% purity) was added to the alkyd resin to which 10% by weight of solvent (methyl ethyl ketone) was added. the alkyd solution was mixed and heated to 60 ° C until the deltamethrin was completely dissolved. The emulsion was prepared at 60 ° C by adding the alkyd solution to the aqueous solution and mixed at high speed (at least 4000 rpm, the larger, the smaller 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 amount 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 amount of the solvent present.

[074] The resulting emulsion was highly similar to those obtained with the indirect method. The particle size distribution (d (0.5) varied between 2 (4% by weight in relation to the total amount of the emulsion surfactant) and 3 (6% by weight of surfactant) microns. The particle size could be varied by changing parameters such as type of surfactants, mixing speed, process temperature or neutralization of the alkyd.

MEASUREMENT OF PARTICLE SIZE DISTRIBUTION

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28/36 [075] 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's theory. In this technique, the particle size is determined by analyzing the dispersion pattern of the particles. The model number is MAL 1024504. The software used was provided by the manufacturer and was version 5.6. The measurement was made using standard operating procedures using a value of 1.54 for the refractive index of the alkyd. A typical measurement involves the following steps: cleaning the dispersion unit, filling with demineralized water, adding a quantity of dispersant (if necessary), circulating the mixture through the bottom level measurement cell, adding an amount of alkyd until an obscuration of 2 to 10% is obtained, measuring the sample 3 times in a row and calculating the average.

DETERMINATION OF DELTAMETRINE ISOMER CONTENT [076] Liquid phase chromatographic methods using a chiral column have been used to resolve the stereoisomers of pyrethroid insecticides such as deltamethrin. Such methods are described, for example, by A. Navas Diaz et al (A. Navas Diaz et al., Journal of Chromatographic Science 1998, 36, pp 210-216) or by R. James Maguire (R. James Maguire, J Agric Food Chem. 1990, 38, pp 1613-1617).

STEM-EDX IMAGE [077] In STEM, a finely focused electron beam (1 nm) is rasterized through a thin sample (50 to 100 nm). At each raster point, both the transmitted electrons and the emitted X-rays are captured. This produces a

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29/36 electron image showing a projection of the area of interest and element maps of the relevant elements. Thin samples of the liquid dispersion were created by sectioning the frozen liquid with an ultramicrotome, followed by evaporation of the water.

[078] A Jeol 2010 FEG TEM, equipped with a Gatan US100 CCD camera, a STEM unit and an EDX analyzer was used for these measurements. The instrument was operated at 200 keV. The EDX analyzer is an SDD detector from Thermo Scientific, which comes with NS6 software for electronic image acquisition and X-ray acquisition and data evaluation.

MEASUREMENT OF BIOLOGICAL EFFICACY USING THE CONE TEST METHOD [079] The cone test was used to determine the bioeffectiveness of materials prepared against mosquitoes. The bioefficiency of the materials is usually expressed in% of mosquitoes knocked over and killed after exposure to panels painted with ink comprising biocide (in this case deltamethrin). The test is described below.

[080] Mosquitoes, Anopheles stephensi, were obtained. Only female mosquitoes aged 2 to 5 days were used in the experiments. Before the test, mosquitoes were supplied with water with sugar, but did not receive a blood meal.

[081] Ten female mosquitoes were confined to a panel painted through a cone (approx. 10 cm in base diameter) for a period of six hours. A piece of cotton was placed around the neck of the cone to prevent mosquitoes from escaping. The panels were tested at an approximate 45 ° angle. After six hours of confinement in the cone, mosquitoes

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30/36 were removed and placed in clean half-liter plastic pots, covered with a woolen net, attached to an elastic band and supplied with sugar water (cotton pad soaked in the sugar solution).

[082] Knockdown and mortality assessments were performed at 0.5, 1, 1.5, 2, 3, 5, 6, 24 and 48 hours after initial exposure. The temperature was typically around 26 ° C ± 3, with relative humidity ranging between 30% and 45% throughout the experimental period. Three replicates were conducted for each panel.

EMULSIONS CONTAINING DELTAMETRINE [083] Using the direct emulsification method, an emulsion was prepared for all 8 alkyds as listed above. The target particle size was set at 5 microns, and some variation in particle size is observed depending on the type of alkyd. No particle size optimization was done. Deltamethrin - a type of pyrethroid insecticide - was used as a biocide at 0.5 and 1.0% by weight. The average particle size for the different emulsions is shown in Figure 1. In this way, the emulsions were obtained with an average particle size d (0.5) varying between 2.3 microns (alkyd number 3; 0.5% in weight of deltamethrin) to 9.1 microns (alkyd number 4; 0.5% by weight of deltamethrin).

[084] In order to prove that deltamethrin was encapsulated in discrete alkyd particles, STEM-EDX imaging was used. The presence of a bromine atom in the deltamethrin molecule provided a useful loop for identification and location of the insecticidal material.

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31/36 [085] STEM-EDX imaging of an emulsion of the invention (alkyd number 5) containing 1% deltamethrin indicated that bromine was limited in location significantly for resin particles with bromine showing to be homogeneous across the particle.

[086] SEM imaging also revealed that deltamethrin was encapsulated in the alkyd matrix, that is, matrix encapsulation, not core peel. In other words, the asset is evenly distributed throughout the alkyd, not located in a structural core / wall. Consequently, in one aspect, the biocide in the emulsion of an alkyd in an aqueous solution of the invention is encapsulated in the matrix in the alkyd.

EMULSION STORAGE STABILITY [087] Emulsion stability through storage is an important property, as it allows longer time between encapsulation and the application of encapsulated biocide, for example, in the formation of paint.

[088] An alkyd number 3 emulsion was prepared using the direct method. After preparation, that is, after 0 days of storage), the average particle size d (0.5) was about 2.3 microns (between 2.0 and 2.5 microns). The emulsion was stored in a closed bottle 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, since the average particle size d (0.5) remained between 2.0 and 2.5 microns.

[089] Likewise, an alkyd number 8 emulsion comprising deltamethrin was stored for 68

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32/36 days. During storage, the average particle size d (0.5) remained stable (i.e., about 4 microns).

[090] In the two emulsions (alkyd number 3 and 8), some resolution of the emulsion was observed during storage, but the emulsions were easily redispersible using a low-shear mixture suggesting that the emulsion droplets are rigid enough to preserve their shape through storage.

STABILITY OF DELTAMETRINE ENCAPSULATED IN ALCHIDIC EMULSIONS [091] The main purpose for encapsulation is to provide the asset (biocide or insecticide such as deltamethrin) with protection against racemization and degradation. After preparation, the samples were stored for three weeks at 54 ° C, which is taken as indicative for three years of aging at room temperature.

[092] Samples were prepared by dosing encapsulated alkyd deltamethrin to an active content level of 0.01% by weight in a white water-based wall paint in the 20 to 80 PVC range (AkzoNobel commercial paint) . The ink was adjusted to pH 8, 9 and 10 and the samples were incubated at 54 ° C for three weeks. HPLC measurements were taken and 0, 4, 7, 10, 14, 17 and 21 days to determine the stability of deltamethrin using the method as described here somewhere. The results were compared with samples containing the standard drop in (deltamethrin as 25 g / L of suspension contracted by Bayer). The ink was adjusted to pH 8, 9 and 10 and the samples were incubated at 54 ° C for three weeks.

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33/36 [093] The results for standard drop-in are shown in Figure 2 which shows the rate of decrease of% of active isomer over time as a function of pH. As expected, more alkaline environments increase the racemization rate with the strongest effect observed at pH 10. This experiment indicated a drop of almost 20% in the active content at pH 9 while at pH 8, the drop was 10% after 21 days of storage (actual measurement was made after 22 days).

[094] The results obtained for samples, where deltamethrin was encapsulated, are shown in Figure 3 for very long oil alkyds (Figure 3A pH = 8; Figure 3B pH = 9 and Figure 30 pH = 10), Figure 4 for alkyds long oils (Figure 4A pH = 8; Figure 4B pH = 9 and Figure 40 pH = 10), and Figure 18 for short, medium and long oil alkyds (Figure 5A pH = 8; Figure 5B pH = 9 and Figure 30 pH = 10). The total encapsulation in the alkyds led to an improvement in stability against racemization especially at pH 8 and 9. At pH 10, the very long alkyds provided some small improvement. Note that especially at pH = 10, racemization begins during preparation. Due to the time between preparation and the first measurement (up to a few hours), the activity of deltamethrin is less than 100%. The acid value did not appear to impact the performance of alkyds as encapsulation media 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 solid alkyds with only 2% by weight of solvent as compared to 35% for long oil alkyds. A lower solvent content is desirable because it adds a penalty of

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Lower VOC and simplifies the production method, as an additional solvent removal step is not required. It also reduces the diffusion of deltamethrin outside the encapsulation that is thought to be mediated by the solvent.

BIOLOGICAL EFFICACY OF BIOCIDES ENCAPSULATED IN ALCHIDIC [095] Encapsulation of deltamethrin in very long oil alkyds improved stability against racemization especially at pH 8 and 9 as shown above. But, for encapsulation to be useful, the active ingredient, in this case deltamethrin, must also have a bioavailability and effectiveness against mosquitoes similar to or better than the standard dropin (from a suspension of 25 g / L of deltamethrin concentrated in the paint). A significantly lower effectiveness against mosquitoes is indicative that the encapsulation is very effective and prevents the migration of deltamethrin to the ink surface.

[096] The biological effect of prepared deltamethrin encapsulations on alkyd number 6 (a medium oil length alkyd) was tested by incorporating the encapsulations in a white water-based wall paint in the 20 to 80 PVC range using a acrylic styrene latex and Optifilm QE300 (Eastman Chemicals) as coalescent and a total deltamethrin content of 0.01% by weight. The particle sizes of the alkyd 6 encapsulation of deltamethrin are shown in Table 1. The films were tested using the cone test method as described here. The bioeffectiveness of the panels tested is expressed as% of mosquitoes dropped and killed after exposure to the panels.

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35/36 [097] Table 1-0 particle size of the different emulsions based on the alkyd number 6

Sample name Particle size d (0.5) [microns] Person number 6 Variant 1 5, 6 Person number 6 Variant 2 9, 1 Person number 6 Variant 5 0.4 Person number 6 Variant 6 2.5 Person number 6 Variant 7 14, 1 Person number 6 Variant 8 6, 6

[098] The bio-efficacy results for the tested variants of deltamethrin encapsulations in alkyd number 6 in white water-based wall paint in the PVC range 20 to 80 were compared to the newly prepared standard drop-in deltamethrin compositions in the same ink formulation (pH = 8, 0.01% by weight of deltamethrin). The results of this comparison are shown in Figure 6.

[099] The results indicate that none of the tested variants performed better than the newly prepared standard drop-in where 95% of mosquitoes are dropped and killed after 5 hours. The alkyd number 6 variants exhibited a wide range of effectiveness against the tested mosquitoes, ranging from weak to variant 6 (40% of mosquitoes dropped and killed after 48 hours) to similar to the standard drop-ín for variant 2 (85% of mosquitoes felled and killed after 6 hours.

[100] In addition, for the bioeffectiveness of the biocide encapsulated in the medium length alkyd, the bioeffectiveness of deltamethrin encapsulated in a very long oil alkyd (alkyd number 5) was tested in a similar manner using the cone test method. The encapsulated material was incorporated into a white water-based wall paint in the PVC range from 20 to 80 using standard vinyl acetate as

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36/36 latex in 0.1% by weight of active level. The test results are shown in Figure 7 and they indicate similar levels of effectiveness against the tested mosquitoes as the ink that just received the drop-ín. The standard drop-ín showed a better efficiency for the initial period, but the difference between the samples is very close to the experimental measurement error.

[101] The above experiments show that the release of the biocide (in these examples, deltamethrin) from a coating composition is sufficient to kill mosquitoes at a similar or slightly lower level as in the newly prepared drop-in composition. The examples further show that the racemization of the biocide is significantly less when it is encapsulated in an alkyd using the method of the invention. The significantly lower levels of racemization compensate for the slight reduction in biological activity due to the encapsulation of the biocide by the alkyd.

ENCAPSULATION OF OTHER ALCHIDIC PESTICIDES [102] The alkyd encapsulation method used for deltamethrin has been tested for other pesticides to determine its viability. Permethrin (cis enantiomer) is another part of biocide of the pyrethroid class of insecticides.

[103] The samples were prepared using very long oil alkyds (numbers 4 and 5) in a process similar to that 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. Thus, emulsions with permethrin have a mean particle size similar to those with deltamethrin.

Claims (15)

1. EMULSION OF AN ALCHIDIC IN AN Aqueous Solution, characterized by the alkyd comprising an optically active biocide and the aqueous solution comprising between 0.1 and 10% by weight of surfactant; wherein the amount of non-aqueous solvent is less than 15% by weight, preferably less than 10 or 5% by weight, and where the pH of the emulsion is between 7 and 11. EMULSION, according to claim 1, characterized in that the length of the alkyd oil is greater than 60%, preferably in which the length of the alkyd oil is greater than 75%. EMULSION, according to claim 1 or 2, wherein the emulsion is characterized between 20 and 60% non-volatile, preferably between 35 and 50% non-volatile. EMULSION, according to any of claims 1 to 3, characterized in that the pH of the emulsion is between 8 and 10, or in which the pH of the emulsion is between 8 and 9. EMULSION, according to any one of claims 1 to 4, characterized in that the amount of the optically active biocide in the emulsion is less than 10% by weight, or in which the amount of the optically active biocide in the emulsion is between 0.01 and 5 % by weight. 6. EMULSION, according to any one of claims 1 to 5, characterized in that the optically active biocide is an optically active insecticide; preferably in which the optically active insecticide is a pyrethroid or pyrethrin; or where the optically active insecticide is a pyrethroid; more preferably the optically active insecticide is selected from the group consisting of permethrin, deltamethrin and Petition 870190101378, of 10/09/2019, p. 46/166 2/3 cypermethrin; even more preferably where the optically active insecticide is deltamethrin. 7. PROCESS FOR PREPARING THE EMULSION, as defined in any of claims 1 to 7, characterized by comprising the steps of: i) supply of an aqueous solution of a surfactant comprising between 0.1 and 10% by weight of the surfactant, ii) supply of an optically active biocide dissolved in an alkyd iii) emulsification of the biocide dissolved in the alkyd of step ii in the aqueous solution of step i, iv) adjusting the pH of the emulsion to a value between 7 and 11, preferably between 8 and 10, or to a value between 8 and 9. PROCESS, according to claim 7, characterized, in step iii, by the emulsion being prepared by adding the aqueous solution in the alkyd or by adding it in the aqueous solution; preferably by adding the alkyd to the aqueous solution. 9. EMULSION OF AN ALQUIDIC IN A WATER SOLUTION, characterized by being obtainable by the process as defined in any of claims 7 or 8. 10. COATING COMPOSITION, characterized in that it comprises the emulsion as defined in one of claims 1 to 6 or 9, in which the amount of non-aqueous solvent is less than 15% by weight and in which the pH of the coating composition is between 7 and 11. 11. COATING COMPOSITION, as defined in claim 9 and according to claim 10, characterized in that the amount of the optically active biocide is between 0.0001 and 5% by weight, or in which the amount of the Petition 870190101378, of 10/09/2019, p. 47/166 3/3 optically active insecticide in the coating composition is between 0.0001 and 5% by weight, preferably where the amount of the optically active biocide is between 0.0001 and 0.1% by weight. 12. COATING COMPOSITION, as defined in claim 9 and according to claim 10 or 11, characterized in that the pH of the coating composition is between 8 and 10, or where the pH of the coating composition is between 8 and 9. 13. SUBSTRATE COATED WITH A COATING OF A COATING COMPOSITION, as defined in any of claims 10 to 12, or a substrate coated with an emulsion characterized by being deposited from the emulsion as defined in any of claims 1 to 6 or 9. 14. COATING PROCESS, characterized in that it comprises the step of coating a substrate with a coating composition as defined in any one of claims 10 to 12. 15. USE OF A COATING COMPOSITION, as defined in any one of claims 10 to 13, characterized in that it is in a varnish, lacquer, paint, coating, stain, enamel, printing ink or floor covering.