WO2016142924A1 - Paint-like coating for controlling vectors - Google Patents

Paint-like coating for controlling vectors Download PDF

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Publication number
WO2016142924A1
WO2016142924A1 PCT/IB2016/051420 IB2016051420W WO2016142924A1 WO 2016142924 A1 WO2016142924 A1 WO 2016142924A1 IB 2016051420 W IB2016051420 W IB 2016051420W WO 2016142924 A1 WO2016142924 A1 WO 2016142924A1
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WO
WIPO (PCT)
Prior art keywords
coating
volume
coating according
pvc
paint
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PCT/IB2016/051420
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Spanish (es)
French (fr)
Inventor
Iván Dario VÉLEZ BERNAL
Raúl Leonardo ROCHA ORJUELA
Olga Elena ROLDÁN CARDONA
María Patricia POSADA JARAMILLO
Antonio Ramón VASCONCELLOS IZQUIERDO
Gilberto LOAIZA DÁVILA
Original Assignee
Universidad De Antioquia (Udea)
Compañia Global De Pinturas S.A.
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Publication of WO2016142924A1 publication Critical patent/WO2016142924A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D131/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02Homopolymers or copolymers of esters of monocarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

  • the present invention belongs to the field of coatings, particularly to the field of paints for indoor or outdoor use.
  • the paint type coating of the invention comprises at least one biocidal agent for the control of disease transmitting pests and insects.
  • Vector-borne diseases are a serious health problem that affects millions of people and cause, in addition to loss of human life, very high costs for fumigation campaigns and other programs for the control of transmitting insects.
  • vectors of diseases such as dengue, malaria and chikungunya have colonized new geographical areas and new outbreaks of these diseases are emerging, thus becoming a priority public health issue (1) .
  • US 5912003 discloses a spray application coating, the formulation of which contains insecticidal agents.
  • this coating is free of pigment, which does not allow to have a decorative function, basic requirement in paints and finishes for domestic use. Additionally, the insecticidal agents used are not harmless to human health.
  • Other formulations, such as those mentioned in US5843215, include insecticidal agents of contact action in combination with repellent agents, which results in the cancellation of the insecticidal effect since, by the effect of the repellent, the insects avoid perching on the treated surfaces.
  • WO 2011045448 describes a paint that includes insecticidal compounds (pyrethroids, carbamates, neonicotinoids, phenylpyrazoles and organophosphates), acaricides, chitin inhibitors and a juvenile hormone regulator in concentrations of up to 20% w / w for pest control.
  • insects The paintings disclosed therein contain binders, pigments, fillers, natural repellents, stabilizers and insecticides are incorporated into the formulation through a microencapsulation process. The insecticides reported there are not safe for health.
  • CA 1291296 discloses concentrates for the preparation of varnishes and vinyl or acrylic paints containing biocidal agents, preferably decamethrin and lindane. The concentrate comprises a saturated medium containing at least one 50% w / w pesticide and a 10% w / w acaricidal agent incorporated in a polar solvent, which is a transport medium not recommended in water-based systems.
  • US 20110015299 mentions a process for incorporating water insoluble biocides (isothiazoles, ortho-phenylphenol, benzimidazoles, chlorothalonil and alkylisothiazolinones) in latex-like paint compositions.
  • water insoluble biocides isothiazoles, ortho-phenylphenol, benzimidazoles, chlorothalonil and alkylisothiazolinones
  • the biocidal agents indicated there are those commonly used for the preservation of paint in the container (control of microorganisms that are generated in aqueous media) but not for the control of insects.
  • the present invention relates to a coating with pesticide action comprising at least one biocidal agent together with additives, binders, preservatives, pigments and fillers, wherein the ratio between the volume of pigment plus the volume of fillers and the total volume of solids it is between 0% and 90%, preferably between 40% and 90% and even more preferably between 60% and 75% whereby the effect of the biocidal agent is enhanced and its effectiveness is increased.
  • the coating of the invention is effective in controlling pests and insects and is substantially harmless to humans and pets.
  • FIG. 1 Structural formula of Permethrin in its cis: trans isomers.
  • FIG. 2 Results of Insecticidal Coating Activity of Example 3.
  • FIG. 3 Correlation between PVC Coating and Efficiency.
  • FIG. 4 Correlation between Emulsion Type vs Knock Down.
  • FIG. 5 Correlation between Emulsion Type vs. Mortality.
  • the present invention relates to a coating comprising at least one biocidal agent together with additives, binders, preservatives, pigments and fillers, wherein the ratio between the volume of pigment plus the volume of fillers and the total volume of solids is between the 0% and 90%, preferably between 40% and 90% and more preferably between 60% and 75% that allows it to fulfill various functionalities such as protecting, beautifying and acting as a means of control and elimination of insects and pests.
  • biocidal agent refers to compounds capable of controlling the proliferation of pests and insects.
  • Different biocidal agents may be included in the coating of the present invention, including pesticides and insecticides, either alone or in combination.
  • the biocidal coating agents are compounds of the pyrethroid family, such as pyrethrin, aletrin, tetramethrin, resmethrin, Phenotrin, permethrin, biphentrin, cypermethrin, fenopropantin, deltamethrin, cifenatrin, fenvarelate, fluvalinat and their mixtures in concentrations from 0.001% to 10.0% w / w, preferably between 0.1% and 5.0% w / w.
  • the biocidal coating agent is permethrin with a ratio of cis: trans 25/75 isomers as illustrated in FIG 1 and in an even more preferred embodiment of the invention, the biocidal agent is Bematin. PER 40 ® from CHT R. Beitlitch GMBH.
  • Permethrin is a pyrethroid of neurotoxic action for insects because it disrupts or blocks the balance of sodium and potassium ions in the walls of the insect's nervous system cells. Under the action of this pyrethroid, the nerve fibers of the insect suffer an electrical imbalance in the ion exchange processes, interrupting the normal transmission of nerve impulses, which causes immediate paralysis in the insect and its subsequent death (2-4). The risks associated with permethrin in humans and warm-blooded animals are negligible, since the molecule is degraded to its inactive metabolites by the esterase enzymes present in the skin. By having a mechanism of action by contact in insects, there is no release of the compound into the environment and does not enter people through the respiratory tract (5,6).
  • Binders also called binders or resins, are the agents that bind and keep the components of the coating together when the film dries.
  • Resins are polymers, generally of the organic type, that form a continuous film when the solvent evaporates and are highly responsible for the adhesion of the system to the substrate. Its chemical nature is significantly linked to the mechanical, strength and durability properties of the final product. (7)
  • the binders of the coatings of the present invention can be dispersed in the aqueous phase forming emulsions with particle sizes of less than 5 ⁇ , where, after evaporating the solvent, the polymer particles coalesce forming a continuous movie.
  • the coatings binders are selected from polyvinyl acetate (PVA), vinyl veova, vinyl acryl veova, ethylene vinyl acrylate, acrylic styrene, pure acrylic and styrene butadiene; vinyl acrylic being the most preferred.
  • pigments Another key component in the composition of a coating is pigments, which are responsible for providing color and coverage in a paint.
  • Pigments which by their chemical nature can be organic or inorganic, are solid particles, finely divided and insoluble in the medium to be dispersed with a refractive index greater than 1.7.
  • the pigments fulfill specific functions in some properties of the paints such as viscosity, brightness, chemical and weather resistance, flame retardant properties, reflection of solar rays, thermal stability, etc.
  • the coating may contain one or more pigments selected from the group consisting of diarylide yellows, hansa yellows, benzimidazolone orange, quinacridone red, phthalocyanine blue, phthalocyanine green, titanium dioxide, oxides of red iron, yellow iron oxides, chromic green and blue based on aluminum silicate, with titanium dioxide being the most preferred.
  • the coating does not contain pigments.
  • Fillers or fillers are defined as insoluble particulate materials in the dispersing medium that do not provide color or coverage in a paint. Generally, they are included in the coatings to increase volume (due to its low density), improve rheology and / or adjust technical properties (hardness, wear resistance, sedimentation control, decantation and impermeability) and generate a greater optical effect on primary pigments .
  • fillers include calcite, dolomite, quartz, barite, diatomaceous earth, polymeric fillers (eg opaque polymers), CaC0 3 (natural or precipitated), talc, kaolin, silica, wollastonite and mixtures thereof (8 , 9).
  • the coating does not contain fillers.
  • the additives refer to those materials that are added in low proportions to improve or impart a specific property on the coating or to adjust some properties.
  • This group includes surfactants, dispersing / wetting Theological additives and defoamers.
  • Surfactants can be anionic or nonionic, those of the non-ionic type, such as octylphenoxyloxylated and nonyl phenol ethoxylated, being the most preferred (9).
  • Theological additives confer the appropriate rheological profile to the product in its different stages. In manufacturing, they help to provide adequate consistency to achieve efficient grinding processes and during storage, improve stability by generating associations between particles that prevent their decantation and also give the product the viscosity required to control the splash and improve leveling and transfer .
  • Theological additives include ethylhydroxyethylcellulose (EHEC), methylcellulose (MC), hydroxyethylcellulose (HEC), ventones, urethane thickeners, associative thickeners and / or mixtures thereof (9).
  • the dispersing agents help to break agglomerates of fillers and pigments and keep said particles away preventing them from agglomerating, while the wetting agents allow to reduce the interfacial tension between the pigment and the vehicle, thus facilitating the wettability of the pigments.
  • dispersing agents polyphosphates, sodium polyacrylates, ammonium polyacrylates, diolacetylene compounds, functionalized polyacrylates and / or mixtures thereof (9) can be used.
  • Synergistic agents are compounds used to enhance the effect of biocidal agents.
  • the coating of the invention may include one or more agents of this type.
  • the coating of the present invention may include coalescing.
  • coalescing applies to those high boiling solvents that act as auxiliaries to facilitate film formation of the system and maintain the plasticity of polymer particles while they deform and coalesce. Once the film is formed, the coalescer evaporates and the system regains its intrinsic hardness.
  • the coalescers are aliphatic hydrocarbons, ethyl glycol dipropylene glycol-n-butylethyl acetate, butyl glycol, hexylene glycol, white spirit, solvesso 150, xylol, varsol, ethylene glycol and / or mixtures thereof (7).
  • Preservatives have the function of protecting the coating against the growth of bacteria, fungi and algae during storage and during its shelf life once applied.
  • the preservatives are selected from the group comprising: tetrahydroxymethyl oxadiazinone, dichlorophenyl dimethylol urea, chloromethyl isothiazolone, methyl isothiazolone and mixtures thereof (7.9).
  • the coating of the present invention may include antifoaming agents to prevent and control foaming during the manufacturing process, including mineral oils, waxes, fatty acid derivatives and silicone derivatives.
  • antifoaming agents to prevent and control foaming during the manufacturing process
  • mineral oils including mineral oils, waxes, fatty acid derivatives and silicone derivatives.
  • other agents such as UV absorbers, antioxidants, plasticizers, anti-decanters and odorizers, selected from those commonly known to one skilled in this technical field (7-9), may be included.
  • the coatings according to the present invention are stable in a pH range between 7.0 and 9.5.
  • Some pH regulating agents such as ammonia and amines can be incorporated into the composition during the process to adjust the pH and reach those values.
  • PVC is closely related to the composition of the dry film and allows to evaluate the morphology of a coating depending on the proportion in which fillers and pigments are present in relation to the binder. If the volume of binder solids is less than the volume of fillers and pigment, it is not possible for the binder to occupy all interstices between particles, resulting in a coating of low cohesion between particles, prone to chalking, low brightness and very porous.
  • a suitable PVC is achieved to guarantee an increase in the effectiveness of the biocidal agent, since the latter, which acts in contact insects, migrates to the surface of the film thus facilitating interaction with insects
  • the additives, binders and pigments used play an important role in the final morphology of the coating and in the value of the CPVC, since they allow obtaining a variety of formulations with similar PVC values and with different arrangements in the packing of loads and porosities.
  • coatings can be obtained without incorporating pigments or fillers, which have a PVC equal to zero.
  • a container provided with a toothed disc must be provided, in which water and the cellulosic thickener are initially added while stirring at low speed until complete solubilization. Then, the dispersing agents, humectants, preservatives, defoamers and coalescers are added, maintaining the agitation until ensuring its total incorporation.
  • the fillings are added and it is completed to volume with water. It is then dispersed at high speed (3500 to 5000 feet / minute) for approximately 30 minutes. Once this has been achieved, the dilution stage is followed, in which the emulsion and pigments are added, maintaining low agitation (80 sec -1 - 500 sec -1 ). Once the homogeneous mixture is obtained, the synergistic agent is added, the pH and viscosity are adjusted by adding pH regulators and thickeners until the desired value is obtained and finally the biocidal agent (s) are added. ).
  • Example 1 Preparation of a coating type paint with 55% ⁇ PVC ⁇ 60% and Copolymer Emulsion Vinyl Acrylic
  • the peripheral velocity (3500 to 5000 feet / minute) was adjusted and dispersed under these conditions for 30 minutes. Then, in order and with low speed stirring (80 sec -1 to 500 sec -1 ), the pigment (titanium sludge), filler (opaque polymer) and the acrylic vinyl copolymer emulsion were added until fully incorporated. The synergistic agent was then added while stirring and the pH was adjusted to 9.0 by adding ammonia. Finally, by systematic additions of the rheological agent, the viscosity was adjusted to a value of (100KU) and the biocidal agent (Perme trina 40% w / w) was added ensuring its total incorporation.
  • Example 2 Preparation of a coating type paint with 60% ⁇ PVC ⁇ 65% and Emulsion Copolymer Vinyl Acrylic
  • Example 3 Preparation of a paint-like coating with 65% ⁇ PVC ⁇ 75% and Copolymer Emulsion Vinyl Acrylic
  • Example 4 Preparation of a coating type paint with 65% ⁇ PVC ⁇ 75% and Emulsion Vinyl Acril Veova
  • Example 5 Preparation of a coating type paint with 65% ⁇ PVC ⁇ 75% and Acrylic Emulsion
  • Example 7 Insecticide activity test Following the cones methodology of WHO 1 , the insecticidal activity of the coating of Example 3 was evaluated under laboratory conditions. For this test a 12 cm diameter plastic cone was placed on a painted specimen with the coating to evaluate. Five female mosquitoes of the Aedes aegypti strain Rockefeller strain, 2 to 5 days old, not fed with blood and raised under conditions of temperature and regulated relative humidity (28 ° C and 80%) were introduced into the cone contact with the surface to be evaluated for 30 minutes.
  • the mosquitoes were removed using a suction pump and placed in a mosquito box with a 10% sugar solution supply. After 1 hour, the Knock Down effect was checked by counting the percentage of mosquitoes that suffered a knockout as a result of contact with the surface under study.
  • Example 8 PVC vs. Effectiveness Correlation Test The correlation between PVC vs. effectiveness was evaluated for coatings with the same type of emulsion and biocide concentration (Examples 1, 2 and 3). The effectiveness results reported by the biological tests for these prototypes show that the higher the porosity of the paint, the greater the insecticide efficacy, as illustrated in FIG 3.
  • Example 9 Correlation test Emulsion Type vs. Effectiveness

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  • Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to a coating having pesticidal activity against pests and insects and with a low hazard potential for humans and pets. The coating comprises at least one biocidal agent and additives, binders, preservatives, pigments and fillers, the relation between the volume of pigment plus the volume of fillers and the total volume of solids (PVC) ranging from 0% to 90%, preferably from 40% to 90%, and most preferably from 60% to 75%.

Description

RECUBRIMIENTO TIPO PINTURA PARA CONTROL DE VECTORES  PAINT TYPE COATING FOR VECTOR CONTROL
CAMPO DE LA INVENCIÓN FIELD OF THE INVENTION
La presente invención pertenece al campo de los recubrimientos, particularmente al campo de las pinturas para uso interior o exterior. El recubrimiento tipo pintura de la invención comprende al menos un agente biocida para el control de plagas e insectos transmisores de enfermedades. The present invention belongs to the field of coatings, particularly to the field of paints for indoor or outdoor use. The paint type coating of the invention comprises at least one biocidal agent for the control of disease transmitting pests and insects.
ANTECEDENTES DE LA INVENCIÓN BACKGROUND OF THE INVENTION
Las enfermedades transmitidas por vectores son un serio problema de salud que afecta a millones de personas y ocasionan, además de pérdida de vidas humanas, altísimos costos destinados a campañas de fumigación y otros programas para el control de los insectos transmisores. En los últimos años, como consecuencia del cambio climático, los vectores de enfermedades como el dengue, la malaria y el chikungunya han colonizado nuevas aéreas geográficas y están apareciendo nuevos focos de estas enfermedades, convirtiéndose así en un tema prioritario de salud pública (1). Vector-borne diseases are a serious health problem that affects millions of people and cause, in addition to loss of human life, very high costs for fumigation campaigns and other programs for the control of transmitting insects. In recent years, as a result of climate change, vectors of diseases such as dengue, malaria and chikungunya have colonized new geographical areas and new outbreaks of these diseases are emerging, thus becoming a priority public health issue (1) .
El control de insectos vectores basados en campañas educativas dirigidas a desmantelar los criaderos al interior de las viviendas o cerca de las mismas, han tenido poco éxito. Algunos métodos tradicionales empleados tales como el uso de toldillos impregnados de insecticida, el uso de repelentes, la fumigación directa de viviendas, la aplicación de larvicidas en los tanques de agua limpia y el control de criaderos, han sido insuficientes para detener el problema. Estos procedimientos mencionados revisten riesgos para la salud, son muy costosos y poco efectivos. Otros procedimientos enfocados en disminuir la población de insectos como esterilización de machos por irradiación resultan demasiado dispendiosos y costosos. En el caso específico de los vectores Aedes Aegypti y Aedes Albopictus , transmisores de dengue y chikungunya, éstos no pican durante la noche sino en horas del día, por lo que el uso de toldillos y mosquiteros no es el más apropiado como medida de prevención, siendo necesario aplicar otras medidas de control para reducir los casos de incidencia de la población en riesgo. The control of vector insects based on educational campaigns aimed at dismantling the hatcheries inside or near the houses, have had little success. Some traditional methods used, such as the use of insecticide-impregnated small poles, the use of repellents, the direct spraying of houses, the application of larvicides in clean water tanks and the control of hatcheries, have been insufficient to stop the problem. These procedures mentioned have health risks, are very expensive and ineffective. Other procedures focused on reducing the population of insects such as irradiation male sterilization are too costly and costly. In the specific case of the Aedes Aegypti and Aedes Albopictus vectors, dengue and chikungunya transmitters, they do not bite during the night but at daylight hours, so the use of small poles and mosquito nets is not the most appropriate as a prevention measure, It is necessary to apply other control measures to reduce cases of incidence of the population at risk.
Para subsanar dichos inconvenientes, se han desarrollado recubrimientos y pinturas con funcionalidad insecticida para uso doméstico y para el sector de la construcción. Sin embargo estos revestimientos pueden ocasionar riesgos elevados para la salud de las personas y mascotas. To overcome these problems, coatings and paints with insecticidal functionality have been developed for domestic use and for the construction sector. However, these coatings can cause high risks to the health of people and pets.
La patente US 5912003 describe un recubrimiento de aplicación por spray, cuya formulación contiene agentes insecticidas. Sin embargo este recubrimiento está exento de pigmento, lo cual no permite tener una función decorativa, requerimiento básico en pinturas y acabados para uso doméstico. Adicionalmente los agentes insecticidas utilizados no son inocuos para la salud de los humanos. Otras formulaciones, tales como las mencionadas en la patente US5843215, incluyen agentes insecticidas de acción por contacto en combinación con agentes repelentes, lo que genera anulación del efecto insecticida ya que, por efecto del repelente, los insectos evitan posarse en las superficies tratadas. US 5912003 discloses a spray application coating, the formulation of which contains insecticidal agents. However, this coating is free of pigment, which does not allow to have a decorative function, basic requirement in paints and finishes for domestic use. Additionally, the insecticidal agents used are not harmless to human health. Other formulations, such as those mentioned in US5843215, include insecticidal agents of contact action in combination with repellent agents, which results in the cancellation of the insecticidal effect since, by the effect of the repellent, the insects avoid perching on the treated surfaces.
El documento WO 2011045448 describe una pintura que incluye compuestos insecticidas (piretroides, carbamatos, neonicotinoides, fenilpirazoles y organofosforados), acaricidas, inhibidores de quitina y un regulador de hormona juvenil en concentraciones de hasta un 20% p/p para el control de plagas e insectos. Las pinturas allí divulgadas contienen, ligantes, pigmentos, cargas, repelentes naturales, estabilizantes y los insecticidas son incorporados en la formulación mediante un proceso de microencapsulación. Los insecticidas allí reportados no son inocuos para la salud. La patente CA 1291296 divulga concentrados para la preparación de barnices y pinturas vinílicas o acrílicas que contienen agentes biocidas, preferiblemente decametrina y lindano. El concentrado comprende un medio saturado que contiene al menos un plaguicida al 50% p/p y un agente acaricida al 10% p/p incorporados en un disolvente polar, el cual es un medio transportador no recomendado en sistemas base agua. WO 2011045448 describes a paint that includes insecticidal compounds (pyrethroids, carbamates, neonicotinoids, phenylpyrazoles and organophosphates), acaricides, chitin inhibitors and a juvenile hormone regulator in concentrations of up to 20% w / w for pest control. insects The paintings disclosed therein contain binders, pigments, fillers, natural repellents, stabilizers and insecticides are incorporated into the formulation through a microencapsulation process. The insecticides reported there are not safe for health. CA 1291296 discloses concentrates for the preparation of varnishes and vinyl or acrylic paints containing biocidal agents, preferably decamethrin and lindane. The concentrate comprises a saturated medium containing at least one 50% w / w pesticide and a 10% w / w acaricidal agent incorporated in a polar solvent, which is a transport medium not recommended in water-based systems.
El documento US 20110015299 menciona un proceso para incorporar biocidas insolubles en agua (isotiazoles, orto-fenilfenol, benzimidazoles, clorotalonil y alquilisotiazolinonas) en composiciones de pintura tipo látex. En dicho documento se describe detalladamente cada uno de los componentes de la composición de la pintura (coalescentes, surfactantes, dispersantes, y pigmentos orgánicos e inorgánicos), así como las fases que los contienen. Los agentes biocidas allí indicados son los utilizados comúnmente para la preservación de la pintura en el envase (control de microorganismos que se generan en medios acuosos) más no para el control de insectos. US 20110015299 mentions a process for incorporating water insoluble biocides (isothiazoles, ortho-phenylphenol, benzimidazoles, chlorothalonil and alkylisothiazolinones) in latex-like paint compositions. This document describes in detail each of the components of the paint composition (coalescing, surfactants, dispersants, and organic and inorganic pigments), as well as the phases that contain them. The biocidal agents indicated there are those commonly used for the preservation of paint in the container (control of microorganisms that are generated in aqueous media) but not for the control of insects.
Si bien en el arte previo se encuentra una amplia variedad de recubrimientos y pinturas que incluyen compuestos pesticidas, éstos no exhiben una eficacia adecuada para el control de insectos vectores ni presentan óptimos márgenes de seguridad para personas y especies animales no objetivo. Although a wide variety of coatings and paints that include pesticidal compounds are found in the prior art, they do not exhibit adequate efficacy for the control of vector insects or present optimal safety margins for non-target animals and animal species.
BREVE DESCRIPCIÓN DEL INVENTO BRIEF DESCRIPTION OF THE INVENTION
La presente invención se refiere a un recubrimiento con acción pesticida que comprende al menos un agente biocida junto con aditivos, ligantes, preservantes, pigmentos y cargas, en donde la relación entre el volumen de pigmento más el volumen de cargas y el volumen total de sólidos está entre el 0% y 90%, preferiblemente entre el 40% y 90% y aún más preferiblemente entre el 60% y 75% con lo cual se potencia el efecto del agente biocida y se aumenta su efectividad. El recubrimiento de la invención es efectivo para controlar plagas e insectos y es sustancialmente inocuo para los humanos y las mascotas. BREVE DESCRIPCIÓN DE LAS FIGURAS The present invention relates to a coating with pesticide action comprising at least one biocidal agent together with additives, binders, preservatives, pigments and fillers, wherein the ratio between the volume of pigment plus the volume of fillers and the total volume of solids it is between 0% and 90%, preferably between 40% and 90% and even more preferably between 60% and 75% whereby the effect of the biocidal agent is enhanced and its effectiveness is increased. The coating of the invention is effective in controlling pests and insects and is substantially harmless to humans and pets. BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 Fórmula Estructural de la Permetrina en sus isómeros cis:trans. FIG. 2 Resultados de Actividad Insecticida del Recubrimiento del Ejemplo 3. FIG. 1 Structural formula of Permethrin in its cis: trans isomers. FIG. 2 Results of Insecticidal Coating Activity of Example 3.
FIG. 3 Correlación entre PVC del Recubrimiento y la Eficacia. FIG. 4 Correlación entre el Tipo de Emulsión vs Knock Down. FIG. 5 Correlación entre el Tipo de Emulsión vs Mortalidad. FIG. 3 Correlation between PVC Coating and Efficiency. FIG. 4 Correlation between Emulsion Type vs Knock Down. FIG. 5 Correlation between Emulsion Type vs. Mortality.
DESCRIPCIÓN DETALLADA DE LA INVENCIÓN DETAILED DESCRIPTION OF THE INVENTION
La presente invención se refiere a un recubrimiento que comprende al menos un agente biocida junto con aditivos, ligantes, preservantes, pigmentos y cargas, en donde la relación entre el volumen de pigmento más el volumen de cargas y el volumen total de sólidos está entre el 0% y 90%, preferiblemente entre el 40% y 90% y más preferiblemente entre el 60% y 75% que le permite cumplir diversas funcionalidades tales como proteger, embellecer y actuar como medio de control y eliminación de insectos y plagas. The present invention relates to a coating comprising at least one biocidal agent together with additives, binders, preservatives, pigments and fillers, wherein the ratio between the volume of pigment plus the volume of fillers and the total volume of solids is between the 0% and 90%, preferably between 40% and 90% and more preferably between 60% and 75% that allows it to fulfill various functionalities such as protecting, beautifying and acting as a means of control and elimination of insects and pests.
Para efectos de la presente invención, el término "agente biocida" se refiere a compuestos con capacidad de controlar la proliferación de plagas e insectos. Diferentes agentes biocidas pueden incluirse en el recubrimiento de la presente invención, entre ellos, plaguicidas e insecticidas, bien sea solos o en combinación. For purposes of the present invention, the term "biocidal agent" refers to compounds capable of controlling the proliferation of pests and insects. Different biocidal agents may be included in the coating of the present invention, including pesticides and insecticides, either alone or in combination.
En una modalidad preferida, los agentes biocidas del recubrimiento son compuestos de la familia de los piretroides, tales como piretrina, aletrina, tetrametrina, resmetrina, fenotrina, permetrina, bifentrin, cipermetrina, fenopropantin, deltametrina, cifenatrin, fenvarelato, fluvalinat y sus mezclas en concentraciones desde 0,001% a 10,0% p/p, preferiblemente entre 0, 1% y 5,0% p/p. En una modalidad más preferida de la invención, el agente biocida del recubrimiento es permetrina con una relación de isómeros cis:trans 25/75 como se ilustra en la FIG 1 y en una modalidad aún más preferida de la invención, el agente biocida es Bematin PER 40® de CHT R. Beitlitch GMBH. In a preferred embodiment, the biocidal coating agents are compounds of the pyrethroid family, such as pyrethrin, aletrin, tetramethrin, resmethrin, Phenotrin, permethrin, biphentrin, cypermethrin, fenopropantin, deltamethrin, cifenatrin, fenvarelate, fluvalinat and their mixtures in concentrations from 0.001% to 10.0% w / w, preferably between 0.1% and 5.0% w / w. In a more preferred embodiment of the invention, the biocidal coating agent is permethrin with a ratio of cis: trans 25/75 isomers as illustrated in FIG 1 and in an even more preferred embodiment of the invention, the biocidal agent is Bematin. PER 40 ® from CHT R. Beitlitch GMBH.
La permetrina es un piretroide de acción neurotoxica para los insectos ya que interrumpe o bloquea el equilibrio de los iones de sodio y potasio en las paredes de las células del sistema nervioso de los insectos. Bajo la acción de este piretroide, las fibras nerviosas del insecto sufren un desequilibrio eléctrico en los procesos de intercambio iónico interrumpiéndose la transmisión normal de los impulsos nerviosos, lo que causa parálisis inmediata en el insecto y su muerte posterior (2-4). Los riesgos asociados a la permetrina en humanos y animales de sangre caliente son insignificantes, puesto que la molécula es degradada a sus metabolitos inactivos por las enzimas estearasas presentes en la piel. Por tener un mecanismo de acción por contacto en los insectos, no hay liberación del compuesto al ambiente y no ingresa a las personas a través de las vías respiratorias (5,6). Permethrin is a pyrethroid of neurotoxic action for insects because it disrupts or blocks the balance of sodium and potassium ions in the walls of the insect's nervous system cells. Under the action of this pyrethroid, the nerve fibers of the insect suffer an electrical imbalance in the ion exchange processes, interrupting the normal transmission of nerve impulses, which causes immediate paralysis in the insect and its subsequent death (2-4). The risks associated with permethrin in humans and warm-blooded animals are negligible, since the molecule is degraded to its inactive metabolites by the esterase enzymes present in the skin. By having a mechanism of action by contact in insects, there is no release of the compound into the environment and does not enter people through the respiratory tract (5,6).
Los ligantes, también llamados binders ó resinas son los agentes que aglutinan y mantienen cohesionados los componentes del recubrimiento cuando la película se seca. Las resinas son polímeros, generalmente de tipo orgánico, que forman una película continua al evaporarse el solvente y son altamente responsables de la adhesión del sistema al sustrato. Su naturaleza química está significativamente ligada a las propiedades mecánicas, de resistencia y durabilidad del producto final. (7) Binders, also called binders or resins, are the agents that bind and keep the components of the coating together when the film dries. Resins are polymers, generally of the organic type, that form a continuous film when the solvent evaporates and are highly responsible for the adhesion of the system to the substrate. Its chemical nature is significantly linked to the mechanical, strength and durability properties of the final product. (7)
Los ligantes de los recubrimientos de la presente invención pueden estar dispersos en la fase acuosa formando emulsiones con tamaño de partículas inferiores a 5 μπι, en donde, luego de evaporarse el solvente, las partículas de polímero coalescen formando una película continua. En una modalidad preferida de la invención, los ligantes de los recubrimientos se seleccionan de polivinil acetato (PVA), vinil veova, vinil acril veova, etileno acrilato de vinilo, estireno acrflico, acrflico puro y estireno butadieno; siendo el vinil acrflico el de mayor preferencia. The binders of the coatings of the present invention can be dispersed in the aqueous phase forming emulsions with particle sizes of less than 5 μπι, where, after evaporating the solvent, the polymer particles coalesce forming a continuous movie. In a preferred embodiment of the invention, the coatings binders are selected from polyvinyl acetate (PVA), vinyl veova, vinyl acryl veova, ethylene vinyl acrylate, acrylic styrene, pure acrylic and styrene butadiene; vinyl acrylic being the most preferred.
Otro componente clave en la composición de un recubrimiento son los pigmentos, los cuáles son los responsables de aportar el color y el cubrimiento en una pintura. Los pigmentos, que por su naturaleza química pueden ser orgánicos o inorgánicos, son partículas sólidas, finamente divididas e insolubles en el medio a dispersar con un índice de refracción mayor a 1,7. Además de su aporte estético, los pigmentos cumplen funciones específicas en algunas propiedades de las pinturas como la viscosidad, brillo, resistencia química y a la intemperie, propiedades ignífugas, reflexión de rayos solares, estabilidad térmica, etc. (7-9) En una modalidad preferida de la invención, el recubrimiento puede contener uno o más pigmentos seleccionados del grupo que consiste de amarillos diarilida, amarillos hansa, naranja bencimidazolona, rojo quinacridona, azul ftalocianina, verde ftalocianina, dioxido de titanio, óxidos de hierro rojo, óxidos de hierro amarillos, verde crómico y azul a base de silicato de aluminio, siendo el dióxido de titanio el más preferido. En otra modalidad preferida de la invención, el recubrimiento no contiene pigmentos. Another key component in the composition of a coating is pigments, which are responsible for providing color and coverage in a paint. Pigments, which by their chemical nature can be organic or inorganic, are solid particles, finely divided and insoluble in the medium to be dispersed with a refractive index greater than 1.7. In addition to their aesthetic contribution, the pigments fulfill specific functions in some properties of the paints such as viscosity, brightness, chemical and weather resistance, flame retardant properties, reflection of solar rays, thermal stability, etc. (7-9) In a preferred embodiment of the invention, the coating may contain one or more pigments selected from the group consisting of diarylide yellows, hansa yellows, benzimidazolone orange, quinacridone red, phthalocyanine blue, phthalocyanine green, titanium dioxide, oxides of red iron, yellow iron oxides, chromic green and blue based on aluminum silicate, with titanium dioxide being the most preferred. In another preferred embodiment of the invention, the coating does not contain pigments.
Los rellenos o cargas se definen como materiales particulados insolubles en el medio dispersante que no aportan color ni cubrimiento en una pintura. Generalmente, se incluyen en los recubrimientos para incrementar volumen (por su baja densidad), mejorar reología y/o ajustar propiedades técnicas (dureza, resistencia al desgaste, control de sedimentación, decantación e impermeabilidad) y generar un mayor efecto óptico a los pigmentos primarios. En una modalidad preferida de la invención, los rellenos incluyen calcita, dolomita, cuarzo, barita, tierra diatomácea, cargas poliméricas (v.g. polímeros opacos), CaC03 (natural o precipitado), talco, caolín, sílica, wollastonita y sus mezclas (8, 9). En otra modalidad preferida de la invención, el recubrimiento no contiene rellenos. Los aditivos hacen alusión a aquellos materiales que se agregan en bajas proporciones para mejorar o impartir una propiedad especifica en el recubrimiento o para ajustar algunas propiedades. A este grupo pertenecen los surfactantes, aditivos Teológicos dispersantes/humectantes y antiespumantes. Los surfactantes pueden ser aniónicos o no- iónicos, siendo los del tipo no-iónicos, tales como los octilfenoletoxilados y nonil fenol etoxilados, los más preferidos (9). Fillers or fillers are defined as insoluble particulate materials in the dispersing medium that do not provide color or coverage in a paint. Generally, they are included in the coatings to increase volume (due to its low density), improve rheology and / or adjust technical properties (hardness, wear resistance, sedimentation control, decantation and impermeability) and generate a greater optical effect on primary pigments . In a preferred embodiment of the invention, fillers include calcite, dolomite, quartz, barite, diatomaceous earth, polymeric fillers (eg opaque polymers), CaC0 3 (natural or precipitated), talc, kaolin, silica, wollastonite and mixtures thereof (8 , 9). In another preferred embodiment of the invention, the coating does not contain fillers. The additives refer to those materials that are added in low proportions to improve or impart a specific property on the coating or to adjust some properties. This group includes surfactants, dispersing / wetting Theological additives and defoamers. Surfactants can be anionic or nonionic, those of the non-ionic type, such as octylphenoxyloxylated and nonyl phenol ethoxylated, being the most preferred (9).
Los aditivos Teológicos confieren el perfil reológico adecuado al producto en sus diferentes estadios. En la fabricación, ayudan a dar la consistencia adecuada para lograr procesos de molturacion eficientes y durante el almacenamiento, mejoran la estabilidad generando asociaciones entre partículas que impiden su decantación y además confieren al producto la viscosidad requerida para controlar el salpique y mejorar la nivelación y transferencia. En una modalidad preferida de la invención, los aditivos Teológicos incluyen etilhidroxietilcelulosa (EHEC), metilcelulosa (MC), hidroxietilcelulosa (HEC), ventonas, espesantes uretánicos, espesantes asociativos y/o mezclas de los mismos (9). Theological additives confer the appropriate rheological profile to the product in its different stages. In manufacturing, they help to provide adequate consistency to achieve efficient grinding processes and during storage, improve stability by generating associations between particles that prevent their decantation and also give the product the viscosity required to control the splash and improve leveling and transfer . In a preferred embodiment of the invention, Theological additives include ethylhydroxyethylcellulose (EHEC), methylcellulose (MC), hydroxyethylcellulose (HEC), ventones, urethane thickeners, associative thickeners and / or mixtures thereof (9).
Los agentes dispersantes ayudan a romper aglomerados de cargas y pigmentos y a mantener alejadas dichas partículas impidiendo que se reaglomeren, en tanto que los agentes humectantes permiten disminuir la tensión interfacial entre el pigmento y el vehículo, facilitando así la humectabilidad de los pigmentos. Como agentes dispersantes se pueden emplear polifosfatos, poliacrilatos de sodio, poliacrilatos de amonio, compuestos diolacetilénicos, poliacrilatos funcionalizados y/o mezclas de los mismos (9). Los agentes sinergísticos son compuestos empleados para potenciar el efecto de los agentes biocidas. El recubrimiento de la invención puede incluir uno o varios agentes de este tipo. Entre los agentes sinergísticos preferidos de la invención se encuentra el butoxido de piperonilo (PBO), el cual inhibe las enzimas del sistema metabólico del insecto permitiendo que el agente biocida permanezca activo por más tiempo (10,11). El recubrimiento de la presente invención puede incluir coalescentes. El término coalescente aplica para aquellos solventes de elevado punto de ebullición que actúan como auxiliares para facilitar la formación de película del sistema y mantener la plasticidad de las partículas de polímero mientas se deforman y coalescen. Una vez formada la película, el coalescente se evapora y el sistema recobra su dureza intrínseca. En una modalidad preferida de la invención, los coalescentes son hidrocarburos alifáticos, dipropilénglicol-n- butileteracetato de etilglicol, butilglicol, hexilenglicol, white spirit, solvesso 150, xilol, varsol, etilén glicol y/o mezclas de los mismos (7). Los agentes preservantes cumplen la función de proteger el recubrimiento contra el crecimiento de bacterias, hongos y algas durante el almacenamiento y durante su vida útil una vez aplicado. En una modalidad preferida de la invención, los preservantes se seleccionan del grupo que comprende: tetrahidroximetil oxadiazinona, diclorofenil dimetilol urea, clorometil isotiazolona, metil isotiazolona y sus mezclas (7,9). The dispersing agents help to break agglomerates of fillers and pigments and keep said particles away preventing them from agglomerating, while the wetting agents allow to reduce the interfacial tension between the pigment and the vehicle, thus facilitating the wettability of the pigments. As dispersing agents, polyphosphates, sodium polyacrylates, ammonium polyacrylates, diolacetylene compounds, functionalized polyacrylates and / or mixtures thereof (9) can be used. Synergistic agents are compounds used to enhance the effect of biocidal agents. The coating of the invention may include one or more agents of this type. Among the preferred synergistic agents of the invention is piperonyl butoxide (PBO), which inhibits the enzymes of the insect's metabolic system allowing the biocidal agent to remain active for a longer time (10,11). The coating of the present invention may include coalescing. The term coalescing applies to those high boiling solvents that act as auxiliaries to facilitate film formation of the system and maintain the plasticity of polymer particles while they deform and coalesce. Once the film is formed, the coalescer evaporates and the system regains its intrinsic hardness. In a preferred embodiment of the invention, the coalescers are aliphatic hydrocarbons, ethyl glycol dipropylene glycol-n-butylethyl acetate, butyl glycol, hexylene glycol, white spirit, solvesso 150, xylol, varsol, ethylene glycol and / or mixtures thereof (7). Preservatives have the function of protecting the coating against the growth of bacteria, fungi and algae during storage and during its shelf life once applied. In a preferred embodiment of the invention, the preservatives are selected from the group comprising: tetrahydroxymethyl oxadiazinone, dichlorophenyl dimethylol urea, chloromethyl isothiazolone, methyl isothiazolone and mixtures thereof (7.9).
El recubrimiento de la presente invención puede incluir agentes antiespumantes para prevenir y controlar la formación de espuma durante el proceso de fabricación, entre ellos, aceites minerales, ceras, derivados de ácidos grasos y derivados de siliconas. De igual manera, se pueden incluir otros agentes tales como absorvedores UV, antioxidantes, plastificantes, antidecantantes y odorizantes, seleccionados de aquellos comúnmente conocidos por un experto en este campo técnico (7-9). The coating of the present invention may include antifoaming agents to prevent and control foaming during the manufacturing process, including mineral oils, waxes, fatty acid derivatives and silicone derivatives. Similarly, other agents such as UV absorbers, antioxidants, plasticizers, anti-decanters and odorizers, selected from those commonly known to one skilled in this technical field (7-9), may be included.
Los recubrimientos de acuerdo a la presente invención son estables en un rango de pH entre 7,0 y 9,5. Algunos agentes reguladores de pH tales como amoníaco y aminas pueden ser incorporados a la composición durante el proceso para ajustar el pH y alcanzar dichos valores. The coatings according to the present invention are stable in a pH range between 7.0 and 9.5. Some pH regulating agents such as ammonia and amines can be incorporated into the composition during the process to adjust the pH and reach those values.
La proporción entre pigmento y ligante en una pintura es determinante en la morfología y propiedades del producto final. Uno de los indicadores más empleados para referirse a la relación entre cargas, pigmentos y ligante en un recubrimiento determinado es el PVC (Pigment Volume Concentration), el cual es el resultado de la relación entre el volumen de pigmento más el volumen de cargas y el volumen total de sólidos, y puede expresarse en porcentaje mediante la siguiente ecuación: (12) The proportion between pigment and binder in a paint is decisive in the morphology and properties of the final product. One of the indicators most used to refer to the relationship between fillers, pigments and binder in a given coating is PVC (Pigment Volume Concentration), which is the result of the relationship between the volume of pigment plus the volume of charges and the total volume of solids, and can be expressed as a percentage by the following equation: (12)
El PVC está estrechamente relacionado con la composición de la película seca y permite evaluar la morfología de un recubrimiento dependiendo de la proporción en la que estén presentes cargas y pigmentos en relación con el ligante. Si el volumen de sólidos de ligante es inferior al volumen de cargas y pigmento, no es posible que el ligante ocupe todos los intersticios entre partículas con lo que se obtiene un recubrimiento de baja cohesión entre partículas, propenso al chalking, de bajo brillo y muy poroso. PVC is closely related to the composition of the dry film and allows to evaluate the morphology of a coating depending on the proportion in which fillers and pigments are present in relation to the binder. If the volume of binder solids is less than the volume of fillers and pigment, it is not possible for the binder to occupy all interstices between particles, resulting in a coating of low cohesion between particles, prone to chalking, low brightness and very porous.
Cuando el volumen de sólidos de resina es justo el suficiente para humedecer y empaquetar cada partícula de pigmento y de cargas y rellenar los espacios vacíos entre ellos se tiene un PVC conocido como CPVC (Critical Pigment Volume Concentration), con el cual se obtiene una película cohesionada, con un brillo entre mate y satinado. Si el PVC de la pintura es inferior al CPVC, se obtiene una película de una porosidad casi nula, en tanto que si el PVC es superior se obtiene una película altamente porosa. When the volume of resin solids is just enough to moisten and pack each particle of pigment and fillers and fill the empty spaces between them there is a PVC known as CPVC (Critical Pigment Volume Concentration), with which a film is obtained cohesive, with a gloss between matte and satin. If the PVC of the paint is lower than the CPVC, a film of almost zero porosity is obtained, while if the PVC is higher, a highly porous film is obtained.
De acuerdo a lo anterior, las propiedades de una pintura presentan cambios dramáticos al acercarse al CPVC. La resistencia a la abrasión, el esfuerzo tensil y la lavabilidad, por ejemplo, decrecen rápidamente cuando se está en las fronteras del CPVC. La permeabilidad y la porosidad son usualmente bajas cuando se está por niveles de PVC inferiores al CPVC, pero se incrementan significativamente al acercarse o sobrepasar este valor. (9,12) According to the above, the properties of a painting show dramatic changes when approaching the CPVC. Abrasion resistance, tensile stress and washability, for example, decrease rapidly when you are at the borders of the CPVC. Permeability and porosity are usually low when PVC levels are lower than CPVC, but they increase significantly as this value approaches or exceeds. (9.12)
Es muy importante establecer una adecuada correlación entre el PVC y la movilidad de los componentes activos del recubrimiento. Experimentalmente se ha encontrado que en un recubrimiento o pintura, las propiedades que son dependientes del movimiento/transporte de materiales a través del recubrimiento, varían dependiendo del PVC. Si el PVC es muy bajo, la porosidad del recubrimiento es muy baja y por lo tanto se disminuye la movilidad de los agentes activos, debido a que el ligante, al ocupar todos los espacios entre las partículas, reduce la cantidad de intersticios que permitan el desplazamiento de los mismos. (13) It is very important to establish an adequate correlation between PVC and the mobility of the active components of the coating. Experimentally it has been found that in a Coating or painting, the properties that are dependent on the movement / transport of materials through the coating, vary depending on the PVC. If the PVC is very low, the porosity of the coating is very low and therefore the mobility of the active agents is reduced, because the binder, by occupying all the spaces between the particles, reduces the amount of interstices that allow the displacement of them. (13)
En los recubrimientos de acuerdo a la presente invención, se logra un PVC adecuado para garantizar un incremento en la efectividad del agente biocida, ya que éste último, que actúa en los insectos por contacto, migra a la superficie de la película facilitando así la interacción con los insectos. Los aditivos, ligantes y pigmentos empleados desempeñan un papel importante en la morfología final del recubrimiento y en el valor del CPVC, ya que permiten obtener una variedad de formulaciones con valores similares de PVC y con arreglos diferentes en el empaquetamiento de cargas y porosidades. En una modalidad preferida de la invención, se pueden obtener recubrimientos sin incorporar pigmentos ni cargas, los cuales tienen un PVC igual a cero. In the coatings according to the present invention, a suitable PVC is achieved to guarantee an increase in the effectiveness of the biocidal agent, since the latter, which acts in contact insects, migrates to the surface of the film thus facilitating interaction with insects The additives, binders and pigments used play an important role in the final morphology of the coating and in the value of the CPVC, since they allow obtaining a variety of formulations with similar PVC values and with different arrangements in the packing of loads and porosities. In a preferred embodiment of the invention, coatings can be obtained without incorporating pigments or fillers, which have a PVC equal to zero.
Para preparar los recubrimientos de la presente invención, se debe disponer de un recipiente dotado de disco dentado, en el cual se adiciona inicialmente agua y el espesante celulósico agitando a baja velocidad hasta solubilización completa. Luego, se adicionan los agentes dispersantes, humectantes, preservantes, antiespumantes y coalescentes, manteniendo la agitación hasta asegurar su total incorporación. To prepare the coatings of the present invention, a container provided with a toothed disc must be provided, in which water and the cellulosic thickener are initially added while stirring at low speed until complete solubilization. Then, the dispersing agents, humectants, preservatives, defoamers and coalescers are added, maintaining the agitation until ensuring its total incorporation.
A la mezcla anterior, se le adicionan los rellenos y se completa a volumen con agua. Luego se dispersa a alta velocidad (3500 a 5000 pies/minuto) durante aproximadamente 30 minutos. Logrado lo anterior, se procede con la etapa de dilución, en la cual se agregan la emulsión y los pigmentos, manteniendo baja agitación (80 seg-1 - 500 seg-1). Una vez obtenida la mezcla homogénea se agrega el agente sinergístico, se ajustan el pH y la viscosidad mediante la adición de reguladores de pH y agentes espesantes hasta obtener el valor deseado y por último se adiciona el(los) agente(s) biocida(s). Si se trata de un recubrimiento con PVC = 0% el proceso se reduce a adicionar a la mezcla que contiene el espesante celulósico ya solubilizado, la emulsión y los demás materiales requeridos, excluyendo los dispersantes y los humectantes. La invención será presentada en detalle a través de los siguientes ejemplos, los cuales son suministrados solamente con propósitos ilustrativos y no con el objetivo de limitar los alcances de la presente invención. To the previous mixture, the fillings are added and it is completed to volume with water. It is then dispersed at high speed (3500 to 5000 feet / minute) for approximately 30 minutes. Once this has been achieved, the dilution stage is followed, in which the emulsion and pigments are added, maintaining low agitation (80 sec -1 - 500 sec -1 ). Once the homogeneous mixture is obtained, the synergistic agent is added, the pH and viscosity are adjusted by adding pH regulators and thickeners until the desired value is obtained and finally the biocidal agent (s) are added. ). If it is a PVC coating = 0% the process is reduced to adding to the mixture containing the already solubilized cellulosic thickener, the emulsion and the other materials required, excluding dispersants and humectants. The invention will be presented in detail through the following examples, which are provided for illustrative purposes only and not for the purpose of limiting the scope of the present invention.
EJEMPLOS EXAMPLES
Ejemplo 1. Preparación de un Recubrimiento tipo pintura con 55% < PVC< 60% y Emulsión Copolímero Vinil Acrílico Example 1. Preparation of a coating type paint with 55% <PVC <60% and Copolymer Emulsion Vinyl Acrylic
Se preparó 1 Litro de recubrimiento tipo pintura, para lo cual se pesaron los siguientes componentes: 1 liter of paint-type coating was prepared, for which the following components were weighed:
Figure imgf000013_0001
En el recipiente de proceso se cargaron 200 g de agua y se adicionó, con agitación a baja velocidad el espesante celulósico hasta su completa solubilización. Luego, se agregaron los agentes dispersantes, humectantes y preservantes hasta su total incorporación. Posteriormente se adicionaron lentamente y con agitación, los rellenos (caolín y talco) y 200 g de agua hasta formar una pasta homogénea.
Figure imgf000013_0001
200 g of water were loaded into the process vessel and the cellulosic thickener was added with low speed stirring until completely solubilized. Then, dispersing agents, humectants and preservatives were added until fully incorporated. Subsequently, the fillings (kaolin and talcum) and 200 g of water were added slowly and with stirring to form a homogeneous paste.
Una vez formada la pasta homogénea, se ajustó la velocidad periférica (3500 a 5000 pies/minuto) y se dispersó bajo estas condiciones durante 30 minutos. Luego se adicionaron, en orden y con agitación a baja velocidad (80 seg-1 a 500 seg-1), el pigmento (lodo de titanio), relleno (polímero opaco) y la emulsión copolímero vinil acrílico hasta total incorporación. Se agregó luego el agente sinergístico manteniendo agitación y se ajustó el pH a 9,0 adicionando amoniaco. Finalmente, mediante adiciones sistemáticas del agente reológico, se ajustó la viscosidad a un valor de (100KU) y se adicionó el agente biocida (Perme trina 40% p/p) asegurando su total incorporación. Once the homogeneous paste was formed, the peripheral velocity (3500 to 5000 feet / minute) was adjusted and dispersed under these conditions for 30 minutes. Then, in order and with low speed stirring (80 sec -1 to 500 sec -1 ), the pigment (titanium sludge), filler (opaque polymer) and the acrylic vinyl copolymer emulsion were added until fully incorporated. The synergistic agent was then added while stirring and the pH was adjusted to 9.0 by adding ammonia. Finally, by systematic additions of the rheological agent, the viscosity was adjusted to a value of (100KU) and the biocidal agent (Perme trina 40% w / w) was added ensuring its total incorporation.
Ejemplo 2. Preparación de un Recubrimiento tipo pintura con 60% < PVC < 65% y Emulsión Copolímero Vinil Acrílico Example 2. Preparation of a coating type paint with 60% <PVC <65% and Emulsion Copolymer Vinyl Acrylic
Siguiendo el mismo procedimiento del Ejemplo 1, se preparó un recubrimiento tipo pintura con los siguientes componentes: Following the same procedure as in Example 1, a paint coating with the following components was prepared:
Figure imgf000014_0001
Pigmento (Lodo de Titanio) 150,0
Figure imgf000014_0001
Pigment (Titanium Mud) 150.0
Emulsión Copolímero Vinil Acrílico 205,0  Emulsion Copolymer Vinyl Acrylic 205.0
Agente sinergístico (BPO) 5,0.0 Synergistic Agent (BPO) 5.0.0
Modificador de pH (Amoníaco) 3,0 PH Modifier (Ammonia) 3.0
Agente Reológico (HASE) 8,0  Rheological Agent (HASE) 8.0
Biocida (Permetrina 40% p/p) 41,0  Biocide (Permethrin 40% w / w) 41.0
Ejemplo 3. Preparación de un Recubrimiento tipo pintura con 65% < PVC < 75% y Emulsión Copolímero Vinil Acrílico Example 3. Preparation of a paint-like coating with 65% <PVC <75% and Copolymer Emulsion Vinyl Acrylic
Siguiendo el mismo procedimiento del Ejemplo 1, se preparó un recubrimiento tipo pintura con los siguientes componentes: Following the same procedure as in Example 1, a paint coating with the following components was prepared:
Figure imgf000015_0001
Ejemplo 4. Preparación de un Recubrimiento tipo pintura con 65% < PVC < 75% y Emulsión Vinil Acril Veova
Figure imgf000015_0001
Example 4. Preparation of a coating type paint with 65% <PVC <75% and Emulsion Vinyl Acril Veova
Siguiendo el mismo procedimiento del Ejemplo 1, se preparó un recubrimiento tipo pintura con los siguientes componentes: Following the same procedure as in Example 1, a paint coating with the following components was prepared:
Figure imgf000016_0001
Figure imgf000016_0001
Ejemplo 5. Preparación de un Recubrimiento tipo pintura con 65% < PVC < 75% y Emulsión Acrílica Example 5. Preparation of a coating type paint with 65% <PVC <75% and Acrylic Emulsion
Siguiendo el mismo procedimiento del Ejemplo 1, se preparó un recubrimiento tipo pintura con los siguientes componentes: COMPONENTE Cantidad (g) Following the same procedure as in Example 1, a paint coating with the following components was prepared: COMPONENT Quantity (g)
Agua 300,0  Water 300.0
Espesante Celulósico 7,0  7.0 Cellulosic Thickener
Dispersante (Poliacrilato de Sodio) 7,0  Dispersant (Sodium Polyacrylate) 7.0
Pigmento (Lodo de titanio) 100,0  Pigment (Titanium Mud) 100.0
Relleno (CaC03, Sílica, Talco y Caolín) 700,0 Filling (CaC0 3 , Silica, Talc and Kaolin) 700.0
Preservante (Ipel BP009) 4,0  Preservative (Ipel BP009) 4.0
Emulsión Acrílica 197,0  Acrylic Emulsion 197.0
Agente sinergístico (BPO) 5,0  Synergistic Agent (BPO) 5.0
Coalescentes (Texanol) 30,0  Coalescers (Texanol) 30.0
Modificador de pH (Amoníaco) 3,0  PH Modifier (Ammonia) 3.0
Agente Reológico (HASE) 5,0  Rheological Agent (HASE) 5.0
Biocida (Permetrina 40% p/p) 41,0  Biocide (Permethrin 40% w / w) 41.0
Ejemplo 6. Preparación de un Recubrimiento tipo pintura con PVC = 0,0% y Emulsión Vinil Acrílica Example 6. Preparation of a paint coating with PVC = 0.0% and Acrylic Vinyl Emulsion
Se preparó 1 Litro de recubrimiento, para lo cual se pesaron los siguientes componentes: 1 liter of coating was prepared, for which the following components were weighed:
Figure imgf000017_0001
Agente Reológico (HASE) 7,0
Figure imgf000017_0001
Rheological Agent (HASE) 7.0
Biocida (Permetrina 40% p/p) 53,0  Biocide (Permethrin 40% w / w) 53.0
En el recipiente de proceso se cargaron 200 g de agua y se adicionó, con agitación a baja velocidad, el espesante celulósico hasta su completa solubilización. Luego se adicionaron, en orden y con agitación a baja velocidad (80 seg-1 a 500 seg-1), los preservantes y la emulsión copolímero vinil acrílico hasta total incorporación. Posteriormente se adicionaron el agente sinergístico y el coalescente manteniendo agitación y se ajustó el pH a 9,0 con solución de amoniaco. Se adicionó el agua restante para finalmente, mediante adiciones sistemáticas del agente reológico, ajustar la viscosidad a un valor de (100KU). Finalmente, se adicionó el agente biocida (Permetrina 40% p/p) con agitación para asegurar su total incorporación. 200 g of water were loaded into the process vessel and the cellulosic thickener was added with low speed stirring until completely solubilized. Then, preservatives and vinyl acrylic copolymer emulsion were added in order and with low speed stirring (80 sec -1 to 500 sec -1 ) until fully incorporated. Subsequently, the synergistic agent and the coalescer were added while stirring and the pH was adjusted to 9.0 with ammonia solution. The remaining water was added to finally, by systematic additions of the rheological agent, adjust the viscosity to a value of (100KU). Finally, the biocidal agent (Permethrin 40% w / w) was added with stirring to ensure its total incorporation.
Ejemplo 7. Ensayo de actividad Insecticida Siguiendo la metodología de conos de la OMS1 se evaluó, en condiciones de laboratorio, la actividad insecticida del recubrimiento del Ejemplo 3. Para esta prueba se posicionó un cono plástico de 12 cm de diámetro sobre una probeta pintada con el recubrimiento a evaluar. Se introdujeron en el cono 5 mosquitos hembras de la especie Aedes aegypti cepa Rockefeller, de 2 a 5 días de edad, no alimentadas con sangre y criadas bajo condiciones de temperatura y humedad relativa regulada (28°C y 80%) y se dejaron en contacto con la superficie a evaluar durante 30 minutos. Example 7. Insecticide activity test Following the cones methodology of WHO 1 , the insecticidal activity of the coating of Example 3 was evaluated under laboratory conditions. For this test a 12 cm diameter plastic cone was placed on a painted specimen with the coating to evaluate. Five female mosquitoes of the Aedes aegypti strain Rockefeller strain, 2 to 5 days old, not fed with blood and raised under conditions of temperature and regulated relative humidity (28 ° C and 80%) were introduced into the cone contact with the surface to be evaluated for 30 minutes.
Al cabo de este tiempo, se retiraron los mosquitos utilizando un succionador y se depositaron en una caja para mosquitos con suministro de solución azucarada al 10%. Transcurrida 1 hora se chequeó el efecto Knock Down contabilizando el porcentaje de mosquitos que sufrieron noqueo por efecto del contacto con la superficie en estudio. After this time, the mosquitoes were removed using a suction pump and placed in a mosquito box with a 10% sugar solution supply. After 1 hour, the Knock Down effect was checked by counting the percentage of mosquitoes that suffered a knockout as a result of contact with the surface under study.
1 WHO: Guidelines for testing mosquito adulticides for indoor residual spraying and treatment of mosquito nets: document WHO/CDS/NTDAVHOPES/GCDPP/2006.3. Geneva: World Health Organization; 2006 Para determinar el porcentaje de mortalidad, se dejan los mosquitos en reposo por espacio de 24 horas a 27 ±2 °C y 80% ±10 HR con solución azucarada. Al cabo de este tiempo se registra el porcentaje de insectos que murieron (Tabla 1). Sobre cada superficie se realizan 10 réplicas usando para cada réplica 5 mosquitos (14). Los resultados obtenidos se ilustran en la FIG 2. 1 WHO: Guidelines for testing mosquito adulticides for indoor residual spraying and treatment of mosquito nets: document WHO / CDS / NTDAVHOPES / GCDPP / 2006.3. Geneva: World Health Organization; 2006 To determine the percentage of mortality, the mosquitoes are left at rest for 24 hours at 27 ± 2 ° C and 80% ± 10 HR with sugar solution. After this time the percentage of insects that died (Table 1) is recorded. On each surface 10 replicas are made using 5 mosquitoes for each replica (14). The results obtained are illustrated in FIG 2.
Tabla 1 Table 1
Figure imgf000019_0001
Figure imgf000019_0001
Ejemplo 8. Ensayo de correlación PVC vs Efectividad Se evaluó la correlación entre PVC vs efectividad para recubrimientos con el mismo tipo de emulsión y concentración de biocida (Ejemplos 1, 2 y 3). Los resultados de efectividad reportados por las pruebas biológicas para estos prototipos muestran que a mayor porosidad de la pintura hay mayor eficacia insecticida, como se ilustra en la FIG 3. Ejemplo 9. Ensayo de correlación Tipo de Emulsión vs Efectividad Example 8. PVC vs. Effectiveness Correlation Test The correlation between PVC vs. effectiveness was evaluated for coatings with the same type of emulsion and biocide concentration (Examples 1, 2 and 3). The effectiveness results reported by the biological tests for these prototypes show that the higher the porosity of the paint, the greater the insecticide efficacy, as illustrated in FIG 3. Example 9. Correlation test Emulsion Type vs. Effectiveness
Se evaluó la correlación entre el tipo de emulsión vs efectividad para recubrimientos con el mismo valor de PVC y concentración de biocida (Ejemplos 3, 4 y 5 con emulsión vinil acrílica, vinil acrílica veova y emulsión acrílica respectivamente). Las pruebas de actividad insecticida mostraron efectividad asociada al tipo de ligante como puede inferirse de las FIG 4 y FIG 5. The correlation between the type of emulsion vs. effectiveness was evaluated for coatings with the same PVC value and biocide concentration (Examples 3, 4 and 5 with vinyl emulsion acrylic, vinyl acrylic veova and acrylic emulsion respectively). The insecticidal activity tests showed effectiveness associated with the type of binder as can be inferred from FIG 4 and FIG 5.
REFERENCIAS REFERENCES
1. Diario El Colombiano www.elcolombiano.com (26/03/2013) 1. El Colombiano newspaper www.elcolombiano.com (03/26/2013)
2. http://es.wikipedia.org/wiki/Piretroide  2. http://en.wikipedia.org/wiki/Piretroide
3. http://es.wikipedia.org/wiki/Permetrina 3. http://en.wikipedia.org/wiki/Permetrina
4. Who Specifications and Evaluations for Public Health Pesticides: Permethrin (25:75 cis : trans isomer ratio)  4. Who Specifications and Evaluations for Public Health Pesticides: Permethrin (25:75 cis: trans isomer ratio)
5. Permethrin_summary_statement  5. Permethrin_summary_statement
6. National Pesticide Telecomunication Network: Pyrethrins & Pyrethroids  6. National Pesticide Telecommunication Network: Pyrethrins & Pyrethroids
7. Heinz Dorr, Dr Franz Holzinger: Bióxido de Titanio Kronos en Pinturas de Emulsión. 1989. 7. Heinz Dorr, Dr Franz Holzinger: Kronos Titanium Dioxide in Emulsion Paints. 1989
8. Detlef Gysau: Fillers for Paints Fundamentáis and Applications. 2006.  8. Detlef Gysau: Fillers for Paints Fundamentalis and Applications. 2006
9. Master en Tecnología de Pinturas. Volumen 1. 1992.  9. Master in Paint Technology. Volume 1. 1992.
10. http://es.wikipedia.org/wiki/But%C3%B3xido de piperonilo  10. http://en.wikipedia.org/wiki/But%C3%B3peroxide piperonyl
11. Faulde Michael, Nehring Oliver: Synergistic Insecticidal and Repellent Effects of Combined Pyrethroid and Repellent-impregnated Bed nets Using a Novel Long- lasting Polymer-coating Multi-layer Technique. Springer-Verlag 2012. Publshed online 20 April 2012. 11. Faulde Michael, Nehring Oliver: Synergistic Insecticidal and Repellent Effects of Combined Pyrethroid and Repellent-impregnated Bed nets Using a Novel Long-lasting Polymer-coating Multi-layer Technique. Springer-Verlag 2012. Publshed online 20 April 2012.
12. Nylen Paul, Sunderland Edward: Modern Surface Cotings. 1965 12. Nylen Paul, Sunderland Edward: Modern Surface Cotings. 1965
13. Master en Tecnología de Pinturas. Volumen 2. 13. Master in Paint Technology. Volume 2

Claims

REIVINDICACIONES
1) Un recubrimiento que comprende al menos un agente biocida junto con aditivos, ligantes, preservantes, pigmentos y cargas, donde la relación entre el volumen de pigmento más el volumen de cargas y el volumen total de sólidos (PVC) del recubrimiento está entre el 0,0% y 90,0% y se determina con la siguiente ecuación: pYQ _ ^Pigmento + VolumenCargas ^ 1) A coating comprising at least one biocidal agent together with additives, binders, preservatives, pigments and fillers, where the ratio between the volume of pigment plus the volume of fillers and the total volume of solids (PVC) of the coating is between the 0.0% and 90.0% and is determined with the following equation: pYQ _ ^ Pigment + Volume Loads ^
Vpigmento +Vcargas +Vsólidos de ligante en donde: Vpigmento = volumen total de pigmentos Vpigmento + Vcarga + Vsolids of binder where: Vpi gme nto = total volume of pigments
Volumen cargas = volumen de cargas  Load volume = load volume
Vsóiidos del ligante = volumen de sólidos de ligante  Vioside of the binder = volume of binder solids
2) Un recubrimiento tipo pintura según la Reivindicación 1, donde el PVC está entre el 55% y 75%. 2) A paint type coating according to Claim 1, wherein the PVC is between 55% and 75%.
3) Un recubrimiento tipo pintura según la Reivindicación 1, que comprende una emulsión de copolímero vinil acrílica y tiene un PVC entre 65% y 70%. 4) Un recubrimiento según la Reivindicación 1 , donde el agente biocida se selecciona del grupo que consiste de piretrinas, piretroides y mezclas de los mismos. 3) A paint type coating according to Claim 1, which comprises an emulsion of vinyl acrylic copolymer and has a PVC between 65% and 70%. 4) A coating according to Claim 1, wherein the biocidal agent is selected from the group consisting of pyrethrins, pyrethroids and mixtures thereof.
5) Un recubrimiento según la Reivindicación 1, donde el agente biocida se selecciona del grupo que consiste de piretrina, aletrina, tetrametrina, resmetrina, fenotrina, permetrina, bifentrin, cipermetrina, fenopropantin, deltametrina, cifenatrin, fenvarelato, fluvalinato y sus mezclas. 5) A coating according to Claim 1, wherein the biocidal agent is selected from the group consisting of pyrethrin, aletrin, tetramethrin, resmethrin, phenotrin, permethrin, biphentrin, cypermethrin, fenopropantin, deltamethrin, cifenatrin, fenvarelate, fluvalinate and mixtures thereof.
6) Un recubrimiento según la Reivindicación 1 , donde el agente biocida es permetrina con una relación de isómeros cis:trans 25/75. 7) Un recubrimiento según la Reivindicación 1, donde la concentración final del agente biocida está entre 0,001% y 10% p/p. 6) A coating according to Claim 1, wherein the biocidal agent is permethrin with a ratio of cis: trans 25/75 isomers. 7) A coating according to Claim 1, wherein the final concentration of the biocidal agent is between 0.001% and 10% w / w.
8) Un recubrimiento tipo pintura según la Reivindicación 1 , que comprende los siguientes componentes: 8) A paint type coating according to Claim 1, comprising the following components:
Figure imgf000023_0001
Figure imgf000023_0001
9) Un recubrimiento según la Reivindicación 1, tipo látex, lavable, de alta resistencia y sustancialmente inocuo, para ser aplicado en superficies tipo paredes y techos. 9) A coating according to Claim 1, latex type, washable, high strength and substantially harmless, to be applied on surfaces such as walls and ceilings.
10) Uso de recubrimiento según la Reivindicación 1, para el control de plagas e insectos transmisores de enfermedades endémicas. 10) Use of coating according to Claim 1, for the control of pests and insects transmitting endemic diseases.
PCT/IB2016/051420 2015-03-12 2016-03-11 Paint-like coating for controlling vectors WO2016142924A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0765365B1 (en) * 1995-04-12 1999-10-20 Surface Coatings International Use of a coating composition with high pigment-volume-concentration
US6881248B2 (en) * 2002-12-30 2005-04-19 Institute For Medical Research Paint composition
CN103965711A (en) * 2014-05-16 2014-08-06 蒋宏宝 Insecticidal environment-friendly emulsion paint

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0765365B1 (en) * 1995-04-12 1999-10-20 Surface Coatings International Use of a coating composition with high pigment-volume-concentration
US6881248B2 (en) * 2002-12-30 2005-04-19 Institute For Medical Research Paint composition
CN103965711A (en) * 2014-05-16 2014-08-06 蒋宏宝 Insecticidal environment-friendly emulsion paint

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FAULDE, M. ET AL.: "Synergistic insecticidal and repellent effects of combined pyrethroid and repellent-impregnated bed nets using a novel long-lasting polymer-coating multi-layer technique.", PARASITOL RES, vol. 111, no. 2, 2012, pages 755 - 765, XP035088351 *
JEROME J. SCHLEIER ET AL: "Green Trends in Insect Control", 2011, article SCHLEIER, J. ET AL.: "Chapter 3: Pyrethrins and Pyrethroid Insecticides.", pages: 95 - 131, XP055308737 *
KIIL, S. ET AL.: "Mathematical Modelling of a self-polishing antifoulding paint exposed to seawater: a parameter study.", CHEMICAL ENGINEERING RESEARCH AND DESIGN, vol. 80, no. 1, 2002, pages 45 - 52, XP022536416, Retrieved from the Internet <URL:http://dx.doi.org/10.1205/026387602753393358> *

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