WO2020237402A1 - Biocide product developed from isothiazolinones and nanoparticles of spherical copper - Google Patents

Biocide product developed from isothiazolinones and nanoparticles of spherical copper Download PDF

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WO2020237402A1
WO2020237402A1 PCT/CL2019/000023 CL2019000023W WO2020237402A1 WO 2020237402 A1 WO2020237402 A1 WO 2020237402A1 CL 2019000023 W CL2019000023 W CL 2019000023W WO 2020237402 A1 WO2020237402 A1 WO 2020237402A1
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copper
product according
biocidal product
biocidal
mixture
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PCT/CL2019/000023
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Spanish (es)
French (fr)
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Ixtiar Begoña MAGUNACELAYA RUMIE
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Protevid Spa
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Priority to PCT/CL2019/000023 priority Critical patent/WO2020237402A1/en
Priority to CL2019001582A priority patent/CL2019001582A1/en
Publication of WO2020237402A1 publication Critical patent/WO2020237402A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper

Definitions

  • copper as a biocidal agent dates back thousands of years, as is the case in ancient Greece, where it was used to treat lung infections and disinfect waters (Dollwet and Sorenson, 1985).
  • copper is used as a biocide both in alloys and in pure form, either in solution or in nanoparticles as part of a polymer.
  • spheroidal copper there are numerous polymer-based products using copper as a biocide, both for domestic and industrial use.
  • the Vequeal company requested the protection by intellectual property of an antimicrobial composition based on Polyvinylpyridone (PVP); Polyethylene glycol (PEG), Polyacrylic Acid (PAA) and spheroidal copper nanoparticles, as well as their use as a coating on solid surfaces for the control of microorganisms, destined for the agro-industry (CL201702277).
  • PVP Polyvinylpyridone
  • PEG Polyethylene glycol
  • PAA Polyacrylic Acid
  • spheroidal copper nanoparticles as well as their use as a coating on solid surfaces for the control of microorganisms, destined for the agro-industry (CL201702277).
  • Isothiazolinones are chemical compounds derived from isothiazole and have been widely described as biocidal agents (Williams, 2017). Among these, the best described compounds regarding their use as biocides are: i) 2-methyl-4-isothiazolin-3-one (MIT); ii) 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT); iii) 1,2-benzisothiazolin-3-one (BIT); iv) 2-n-octyl-4-isothiazolin-3-one (OIT); v) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) (Williams, 2007).
  • MIT 2-methyl-4-isothiazolin-3-one
  • CMIT 5-chloro-2-methyl-4-isothiazolin-3-one
  • BIT 1,2-benzisothiazolin-3-one
  • OIT 2-n-
  • isothiazolinones lies mainly in the creation of cosmetics, beauty products, cutting oils, latex emulsions and tempera paints, among others (Mark et al., 1993, Fernández et al., 2007).
  • MIT and CMIT have been described as fungicidal sources (Pedras and Suchy, 2006; Adibpour et al., 2007; Vicentini et al., 2011), bactericides -gram positive and gram negative- (Pucci et al., 2007 and 2011), viricides (Sharmeen et al., 2001) and algaecides (Khalaj et al., 2004).
  • the mechanism of action of isothiazolinones generally consists of two steps. The first occurs in minutes after contact and consists of the inhibition of various key enzymes for cell growth and metabolism due to their reaction with the thiol groups (SH-) present. Some of these, pyruvate dehydrogenase; succinate dehydrogenase; lactate dehydrogenase; NADH dehydrogenase; among other. The second step occurs several hours later and consists of the cell death of microorganisms due to the accumulation of free radicals as a result of the inhibition of metabolism and cell repair mechanisms (Williams, 2007).
  • the proposed invention consists of a biocidal product developed from a mixture of 4-isothiazolin-3-one and spheroidal copper nanoparticles, which would not be in solution but would instead form a plastic film together with carboxymethylcellulose (CMC) as thickener and stabilizer , preventing the formation of biofilms that cause the detachment of Copper particles, generating traces and a decrease in their useful half-life.
  • CMC carboxymethylcellulose
  • Copper is one of the most widely used metals in industry, both in pure form and in alloys. However, it is susceptible to different forms of corrosion due to the effect of both reactive chemical species sulfates, chlorides, nitrates, etc. and microorganisms (Ramesh and Rajeswari, 2005; Revie, 2008). The latter have been described as capable of forming biofilms, which increase the corrosion potential of copper (Williams et al., 2001).
  • the film obtained differs from the state of the art in the first place, because it is not in solution, but stabilized thanks to the incorporation of carboxymethylcellulose (CMC), which allows an easy and simple application to different materials and with the absence of waste in its process.
  • CMC carboxymethylcellulose
  • this product is distinguished from the state of the art in that, for its correct application, it only requires the incorporation of a single layer of the product to the material to which it is intended to give biocidal attributes. This is due to the fact that all its active principles are found in this polymer, without the need to add other agents by incorporating other layers.
  • plastic film that is formed from the aforementioned mixture allows the free passage of copper ions through it, thus allowing its biocidal capacity to expand effectively and permanently.
  • this product lacks toxic and / or harmful compounds for health and the environment such as formaldehyde, which is commonly used as a hardener and stabilizer in the preparation of industrial polymers and whose carcinogenic activity is highly described (Act., R., 2011).
  • Nanoparticle interaction with biological membranes does nanotechnology present a Janus face ?. Accounts of Chemical research, 40 (5), 335-342.
  • Methylchloroisothiazolinone / methylisothiazolinone (Kathon CG) biocide second United States multicenter study of human skin sensitization. Dermatitis, 4 (2), 87-89.

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

Abstract

The invention relates to a biocide product developed from a mixture of derivatives of 4-isothiazolin-3-one and nanoparticles of spheroidal copper, forming a single-layer plastic film, together with carboxymethyl cellulose (CMC) as a thickener and stabiliser that allows copper ions to pass freely therethrough. The synergy developed from the mixture of these three compounds increases the average shelf life of the product and the duration and intensity of its biocide effect.

Description

PRODUCTO BIOCIDA DESARROLLADO A PARTIR DE ISOTIAZOLINONAS Y BIOCIDAL PRODUCT DEVELOPED FROM ISOTHIAZOLINONES AND
NANOPARTÍCULAS DE COBRE ESFEROIDALSPHEROIDAL COPPER NANOPARTICLES
MEMORIA DESCRIPTIVA DESCRIPTIVE MEMORY
DESCRIPCIÓN DE LO CONOCIDO DESCRIPTION OF THE KNOWN
I. Cobre esferoidal. I. Spheroidal copper.
EE uso del cobre como agente biocida se remonta a miles de años atrás, como es el caso de la antigua Grecia, donde era utilizado para tratar infecciones pulmonares y desinfectar aguas (Dollwet y Sorenson, 1985). Actualmente el cobre es utilizado como biocida tanto en aleaciones como en forma pura, ya sea en solución como en nanopartículas formando parte de un polímero. The use of copper as a biocidal agent dates back thousands of years, as is the case in ancient Greece, where it was used to treat lung infections and disinfect waters (Dollwet and Sorenson, 1985). Currently copper is used as a biocide both in alloys and in pure form, either in solution or in nanoparticles as part of a polymer.
Se ha reportado que el mecanismo asociado a su actividad como biocida se explica principalmente por 3 fenómenos: I) Liberación de iones de cobre; ii) Liberación de nanopartículas de cobre; iii) Inhibición de la formación de biopelículas (Borkow y Gabbay, 2005; Tamayo y cols., 2016). It has been reported that the mechanism associated with its activity as a biocide is mainly explained by 3 phenomena: I) Release of copper ions; ii) Release of copper nanoparticles; iii) Inhibition of biofilm formation (Borkow and Gabbay, 2005; Tamayo et al., 2016).
Respecto a la liberación de iones cobre, se ha reportado que la transición redox entre Cu2+ y Cu1+ puede catalizar la producción de numerosas especies reactivas, las cuales pueden alterar la permeabilidad de la pared celular y membrana plasmática y dañar subsecuentemente lípidos, ADN, proteínas y otras biomoléculas presentes en microorganismos (Borkow y Gabbay, 2005). También se ha reportado la difusión y endocitosis de nanopartículas de cobre (Leroueil y cols., 2007; Zhang y cols., 2009). Finalmente, respecto a la formación de biopelículas, se ha reportado que el cobre altera la composición de la pared celular y la hidrofobicidad de esta, impidiendo la adhesión normal de las bacterias (Lewis Oscar y cols., 2015). Regarding the release of copper ions, it has been reported that the redox transition between Cu2 + and Cu1 + can catalyze the production of numerous reactive species, which can alter the permeability of the cell wall and plasma membrane and subsequently damage lipids, DNA, proteins and other biomolecules present in microorganisms (Borkow and Gabbay, 2005). The diffusion and endocytosis of copper nanoparticles has also been reported (Leroueil et al., 2007; Zhang et al., 2009). Finally, regarding the formation of biofilms, it has been reported that copper alters the composition of the cell wall and its hydrophobicity, preventing the normal adhesion of bacteria (Lewis Oscar et al., 2015).
Existen numerosos productos basados en polímeros utilizando cobre como biocida, tanto para uso doméstico como industrial. Respecto del cobre esferoidal, la empresa Vequeal solicitó la protección mediante propiedad intelectual de una Composición antimicrobiana en base a Polivinilpirridona (PVP); Polietilenglicol (PEG), Ácido Poliacrílico (PAA) y nanopartículas de cobre esferoidal, así como su uso como recubrimiento sobre superficies sólidas para el control de microorganismos, destinada a la agroindustria (CL201702277). There are numerous polymer-based products using copper as a biocide, both for domestic and industrial use. Regarding spheroidal copper, the Vequeal company requested the protection by intellectual property of an antimicrobial composition based on Polyvinylpyridone (PVP); Polyethylene glycol (PEG), Polyacrylic Acid (PAA) and spheroidal copper nanoparticles, as well as their use as a coating on solid surfaces for the control of microorganisms, destined for the agro-industry (CL201702277).
II. Isotiazolinonas. II. Isothiazolinones.
Las isotiazolinonas son compuestos químicos derivados de isotiazol y han sido ampliamente descritos como agentes biocidas (Williams, 2017). Dentro de estas, los compuestos mejor descritos respecto a su uso como biocidas son: i) 2-metil-4-isotiazolin- 3-ona (MIT); ii) 5-cloro-2-metil-4-isotiazolin-3-ona (CMIT); iii) 1,2 benzisotiazolin-3-ona (BIT); iv) 2-n-octil-4-isotiazolin-3-ona (OIT); v) 4,5-dicloro-2-n-octil-4-isotiazolin-3-ona (DCOIT) (Williams, 2007). Isothiazolinones are chemical compounds derived from isothiazole and have been widely described as biocidal agents (Williams, 2017). Among these, the best described compounds regarding their use as biocides are: i) 2-methyl-4-isothiazolin-3-one (MIT); ii) 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT); iii) 1,2-benzisothiazolin-3-one (BIT); iv) 2-n-octyl-4-isothiazolin-3-one (OIT); v) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) (Williams, 2007).
El uso de las isotiazolinonas se radica principalmente en la creación de cosméticos, productos de belleza, aceites de corte, emulsiones de látex y pinturas al temple, entre otras (Mark y cols., 1993, Fernández y cols., 2007). The use of isothiazolinones lies mainly in the creation of cosmetics, beauty products, cutting oils, latex emulsions and tempera paints, among others (Mark et al., 1993, Fernández et al., 2007).
Recientemente, se ha descrito el uso de MIT de manera aislado como biocida en sistemas de agua industrial, utilizado principalmente como preservante a largo plazo, inclusive a rangos altos de pH y temperatura (US7699995B2). El MIT y CMIT han sido descritos como fuentes fungicidas (Pedras y Suchy, 2006; Adibpour y cols., 2007; Vicentini y cols., 2011), bactericidas -gram positivas y gram negativas- (Pucci y cols., 2007 y 2011), viricidas (Sharmeen y cols., 2001) y alguicidas (Khalaj y cols., 2004). Recently, the use of MIT in isolation as a biocide in industrial water systems has been described, mainly used as a long-term preservative, even at high pH and temperature ranges (US7699995B2). MIT and CMIT have been described as fungicidal sources (Pedras and Suchy, 2006; Adibpour et al., 2007; Vicentini et al., 2011), bactericides -gram positive and gram negative- (Pucci et al., 2007 and 2011), viricides (Sharmeen et al., 2001) and algaecides (Khalaj et al., 2004).
El mecanismo de acción de las isotiazolinonas en general consta de dos pasos. El primero ocurre en minutos luego del contacto y Consiste en la inhibición de diversas enzimas claves para el crecimiento y metabolismo celular debido a su reacción con los grupos tioles (SH-) presentes. Algunas de estas, piruvato deshidrogenasa; succinato deshidrogenasa; lactato deshidrogenasa; NADH deshidrogenasa; entre otras. El segundo paso ocurre varias horas después y consiste en la muerte celular de los microorganismos debido a la acumulación de radicales libres producto de la inhibición del metabolismo y los mecanismo de reparación celular (Williams, 2007). The mechanism of action of isothiazolinones generally consists of two steps. The first occurs in minutes after contact and consists of the inhibition of various key enzymes for cell growth and metabolism due to their reaction with the thiol groups (SH-) present. Some of these, pyruvate dehydrogenase; succinate dehydrogenase; lactate dehydrogenase; NADH dehydrogenase; among other. The second step occurs several hours later and consists of the cell death of microorganisms due to the accumulation of free radicals as a result of the inhibition of metabolism and cell repair mechanisms (Williams, 2007).
Actualmente se encuentran en el mercado diversos productos patentados en base a isotiazolinonas, entre los cuales destacan los siguientes productos: i) Kathon WT 1,5% Microbicide (Rohm and Haas Company; Philadelphia, PA) que consiste en una mezcla 3:1 de CMIT/MIT; ii) Klarix 4000 Microbicide (Rohm and Haas Company; Philadelphia, PA), el cual contiene DCOIT al 4,5% en una microemulsión basada en agua: iii) Kordex MLX Microbicide (Rohm and Haas Company; Philadelphia, PA), el cual contiene MIT al 9,5%. Currently, various patented products based on isothiazolinones are on the market, among which the following products stand out: i) Kathon WT 1.5% Microbicide (Rohm and Haas Company; Philadelphia, PA) consisting of a 3: 1 mixture of CMIT / MIT; ii) Klarix 4000 Microbicide (Rohm and Haas Company; Philadelphia, PA), which contains 4.5% DCOIT in a water-based microemulsion: iii) Kordex MLX Microbicide (Rohm and Haas Company; Philadelphia, PA), which contains 9.5% MIT.
III. Efecto sinérgico entre el cobre y las isotiazolinonas. III. Synergistic effect between copper and isothiazolinones.
Se ha descrito que las isotiazolinonas tienden a degradarse con facilidad en ambientes acuosos, por lo cual se suelen agregar solventes para mejorar su estabilidad. En ese sentido existen patentes relacionadas al usó de nitritos (US4067878); peróxido de hidrógeno (US5153213) y solventes orgánicos como el formaldehído (US 4129448) y (US4165318) con el fin de estabilizarlas. Sin embargo, muchos de estos solventes son altamente tóxicos y cancerígenos, como el caso del formaldehído (Act. R., 2011). Es por eso que en los últimos años se han buscado estabilizantes menos nocivos para el ser humano y el medio ambiente. Uno de ellos es el cobre (II), respecto del cual se han registrado numerosas patentes relativas al uso de iones de cobre no quelados como estabilizantes de MIT, BIT y CMIT (ES2535610T3). Sin embargo, la mayoría de estos reportes hacen hincapié solamente en el efecto del cobre sobre las isotiazolinonas en solución, lo que no resuelve el problema de impedir la formación de biofilms que acarreen la corrosión de las nanopartículas de Cobre. Isothiazolinones have been reported to degrade easily in aqueous environments, so solvents are often added to improve their stability. In this sense, there are patents related to the use of nitrites (US4067878); hydrogen peroxide (US5153213) and organic solvents such as formaldehyde (US 4129448) and (US4165318) in order to stabilize them. However, many of these solvents are highly toxic and carcinogenic, as is the case with formaldehyde (Act. R., 2011). That is why in recent years less harmful stabilizers for humans and the environment have been sought. One of them is copper (II), for which numerous patents have been registered regarding the use of non-chelated copper ions as stabilizers for MIT, BIT and CMIT (ES2535610T3). However, most of these reports emphasize only the effect of copper on isothiazolinones in solution, which does not solve the problem of preventing the formation of biofilms that lead to corrosion of copper nanoparticles.
DESCRIPCIÓN DE LA INVENCIÓN DESCRIPTION OF THE INVENTION
La invención propuesta consiste en un producto biocida desarrollado a partir de una mezcla de 4-isotiazolin-3-ona y nanopartículas de cobre esferoidal, que no estarían en solución sino que formando una película plástica en conjunto con carboximetilcelulosa (CMC) como espesante y estabilizante, impidiendo la formación de biofilms que provocan el desprendimiento de las partículas de Cobre, generando trazas y una disminución en su vida media útil. The proposed invention consists of a biocidal product developed from a mixture of 4-isothiazolin-3-one and spheroidal copper nanoparticles, which would not be in solution but would instead form a plastic film together with carboxymethylcellulose (CMC) as thickener and stabilizer , preventing the formation of biofilms that cause the detachment of Copper particles, generating traces and a decrease in their useful half-life.
El cobre es uno de los metales más utilizados en la industria, tanto en forma pura como en aleaciones. Sin embargo, es susceptible a diferentes formas de corrosión debido al efecto, tanto de especies reactivas químicas sulfatos, cloruros, nitratos, etc. como de microorganismos (Ramesh y Rajeswari, 2005; Revie, 2008). Se ha descrito que estos últimos son capaces de formar biopelículas, las cuales aumentan el potencial de corrosión del cobre (Williams y cols., 2001). Copper is one of the most widely used metals in industry, both in pure form and in alloys. However, it is susceptible to different forms of corrosion due to the effect of both reactive chemical species sulfates, chlorides, nitrates, etc. and microorganisms (Ramesh and Rajeswari, 2005; Revie, 2008). The latter have been described as capable of forming biofilms, which increase the corrosion potential of copper (Williams et al., 2001).
Ahora bien, está ampliamente descrito el uso industrial de diversos biocidas para evitar la corrosión del cobre (aldehidos, glutaraldehídos, amonios cuaternario, etc) pero se ha demostrado que las isotiazolinonas tienen una eficacia superior en la eliminación de bacterias reductoras de sulfato (SRB) y otros organismos debido a los mecanismos antes descritos (Williams y cols., 2001), los cuales son las principales responsables en la formación de biopelículas que corroen el cobre. Sólo a modo de ejemplo, el Desulfovibrio spp es una de las SRB más comunes y está presente en las biopelículas que corroen el cobre. Al respecto se ha demostrado que el uso de isotiazolinonas disminuye notoriamente la corrosión provocada por esta bacteria (Onan y cols., 2010). Now, the industrial use of various biocides to prevent the corrosion of copper (aldehydes, glutaraldehydes, quaternary ammoniums, etc.) has been widely described, but it has been shown that isothiazolinones have a superior efficiency in the elimination of sulfate reducing bacteria (SRB) and other organisms due to the mechanisms described above (Williams et al., 2001), which are the main responsible in the formation of biofilms that corrode copper. Just as an example, Desulfovibrio spp is one of the most common SRBs and is present in biofilms that corrode copper. In this regard, it has been shown that the use of isothiazolinones markedly reduces the corrosion caused by this bacterium (Onan et al., 2010).
A partir de los antecedentes citados y de la investigación desarrollada por Protevid, se obtuvo un producto único y novedoso que consiste en una mezcla de nanopartículas de cobre esferoidal y derivados de la 4-isotiazolin-3-ona que en determinadas proporciones y conformando un mismo polímero, conjuntamente con carboximetilcelulosa (CMC) como espesante y estabilizante, forman una película plástica. From the aforementioned antecedents and the research developed by Protevid, a unique and novel product was obtained consisting of a mixture of spheroidal copper nanoparticles and 4-isothiazolin-3-one derivatives that in certain proportions and forming the same polymer, together with carboxymethyl cellulose (CMC) as a thickener and stabilizer, form a plastic film.
La película obtenida se distingue del estado de la técnica en primer lugar, porque no se encuentra en solución, sino que estabilizada gracias a la incorporación de la carboximetilcelulosa (CMC), lo que permite una aplicación fácil y sencilla a distintos materiales y con ausencia de mermas en su proceso. The film obtained differs from the state of the art in the first place, because it is not in solution, but stabilized thanks to the incorporation of carboxymethylcellulose (CMC), which allows an easy and simple application to different materials and with the absence of waste in its process.
En segundo lugar, el presente producto se distingue del estado del arte en que, para su correcta aplicación, únicamente se requiere de la incorporación de una sola capa del producto al material al cual se pretende dar atributos biocidas. Esto se debe a que en este polímero se encuentran todos sus principios activos, sin necesidad de agregar otros agentes mediante la incorporación de otras capas. Second, this product is distinguished from the state of the art in that, for its correct application, it only requires the incorporation of a single layer of the product to the material to which it is intended to give biocidal attributes. This is due to the fact that all its active principles are found in this polymer, without the need to add other agents by incorporating other layers.
En tercer lugar podemos agregar que la película plástica que se forma a partir de la mezcla ya señalada permite el libre paso de los iones de cobre a través de ésta, permitiendo así que se su capacidad biocida se expanda en forma efectiva y permanente. Thirdly, we can add that the plastic film that is formed from the aforementioned mixture allows the free passage of copper ions through it, thus allowing its biocidal capacity to expand effectively and permanently.
Además cabe destacar que él presente producto carece de compuestos tóxicos y/o nocivos para la salud y medio ambiente tales como el formaldehído, el cual es comúnmente utilizado como endurecedor y estabilizador en la preparación de polímeros industriales y cuya actividad carcinógena está altamente descrita (Act., R., 2011). It should also be noted that this product lacks toxic and / or harmful compounds for health and the environment such as formaldehyde, which is commonly used as a hardener and stabilizer in the preparation of industrial polymers and whose carcinogenic activity is highly described (Act., R., 2011).
En sexto lugar, se ha logrado demostrar que, de la sinergia producida entre sus componentes se ha obtenido una prolongación de la vida media útil del cobre esferoidal al impedir la formación de biofilms que corroen su superficie. Esto a su vez deriva en la disminución de las trazas de cobre generadas producto de su desgaste, lo que a su vez disminuye el impacto ambiental que genera la aplicación de este tipo de productos. Sixthly, it has been possible to show that, from the synergy produced between its components, an extension of the useful half-life of spheroidal copper has been obtained by preventing the formation of biofilms that corrode its surface. This in turn leads to a reduction in the traces of copper generated as a result of its wear, which in turn reduces the environmental impact generated by the application of this type of product.
Finalmente, la sinergia lograda entre sus componentes presente un efecto biocida muy superior a la suma de todos ellos, lo que se manifiesta tanto en la duración de dicho efecto como én su intensidad. Finally, the synergy achieved between its components presents a biocidal effect much higher than the sum of all of them, which is manifested both in the duration of said effect and in its intensity.
BIBLIOGRAFÍA BIBLIOGRAPHY
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Claims

PLIEGO DE REIVINDICACIONES LETTER OF CLAIMS
1. Producto biocida CARACTERIZADO porque se desarrolla a partir de una mezcla de nanopartículas de cobre esferoidal y derivados de la 4-isotiazolin-3-ona. 1. Biocidal product CHARACTERIZED because it is developed from a mixture of spheroidal copper nanoparticles and derivatives of 4-isothiazolin-3-one.
2. Producto biocida según reivindicación 1 CARACTERIZADO porque la mezcla de cobre esferoidal y derivados de la 4-isotiazolin-3-ona hace que formen un sólo polímero o una única solución. 2. Biocidal product according to claim 1 CHARACTERIZED in that the mixture of spheroidal copper and derivatives of 4-isothiazolin-3-one makes them form a single polymer or a single solution.
3. Producto biocida según reivindicaciones 1 y 2 CARACTERIZADO porque en lugar de agregar solventes para estabilizar tanto el cobre como los derivados de 4-isotiazolin- 3-ona, se utiliza carboximetilcelulosa (CMC) como espesante y estabilizante, formando una película plástica. 3. Biocidal product according to claims 1 and 2 CHARACTERIZED because instead of adding solvents to stabilize both copper and 4-isothiazolin-3-one derivatives, carboxymethylcellulose (CMC) is used as thickener and stabilizer, forming a plastic film.
4. Producto biocida según reivindicación 3 CARACTERIZADO porque la película generada contiene todos sus principios activos y no requiere de la aplicación de múltiples capas, destacando la simpleza de su preparación y escalabilidad. 4. Biocidal product according to claim 3 CHARACTERIZED because the film generated contains all its active principles and does not require the application of multiple layers, highlighting the simplicity of its preparation and scalability.
5. Producto biocida según reivindicaciones 1 y 2 CARACTERIZADO porque está libre de componentes tóxicos, cancerígenos y/o nocivos para la salud y/o el medio ambiente, tales como el formaldehído. 5. Biocidal product according to claims 1 and 2 CHARACTERIZED because it is free of toxic, carcinogenic and / or harmful components for health and / or the environment, such as formaldehyde.
6. Producto biocida según reivindicaciones 1 y 2 CARACTERIZADO porque la mezcla entre sus componentes permite potenciar la capacidad biocida del cobre toda vez que, por un lado inhibe diversas enzimas claves para el crecimiento y metabolismo celular del microorganismo, y por el otro, gatilla la muerte celular debido a la acumulación de radicales libres producto de la inhibición del metabolismo y los mecanismos de reparación celular. 6. Biocidal product according to claims 1 and 2 CHARACTERIZED because the mixture between its components allows to enhance the biocidal capacity of copper since, on the one hand, it inhibits various key enzymes for the growth and cellular metabolism of the microorganism, and on the other, it triggers the cell death due to the accumulation of free radicals product of the inhibition of metabolism and cellular repair mechanisms.
7. Producto biocida según reivindicaciones 1, 2, y 6 CARACTERIZADO porque la mezcla entre sus componentes previene a su vez la corrosión del cobre, favoreciendo su integridad y aumentando su vida media útil al inhibir la aparición de biofims. Al evitar la corrosión del cobre hay una notoria disminución de las trazas de cobre. 7. Biocidal product according to claims 1, 2, and 6 CHARACTERIZED because the mixture between its components in turn prevents corrosion of copper, favoring its integrity and increasing its useful half-life by inhibiting the appearance of biofims. By avoiding the corrosion of copper there is a noticeable decrease in traces of copper.
8. Producto biocida según reivindicaciones 1, 2, 3, 4, 5 y 6 CARACTERIZADO porque la mezcla entre sus componentes en determinadas proporciones produce un efecto sinérgico superior al aumentar, tanto la duración de su efecto antimicrobiano como su intensidad. 8. Biocidal product according to claims 1, 2, 3, 4, 5 and 6 CHARACTERIZED in that the mixture of its components in certain proportions produces a superior synergistic effect by increasing both the duration of its antimicrobial effect and its intensity.
9. Producto biocida según reivindicaciones 1, 2, 3, 4, 5, 6, 7 y 8 CARACTERIZADO porque la película aplicada permite el libre paso de los iones de cobre a través de ella, permitiendo que este actúe libremente. 9. Biocidal product according to claims 1, 2, 3, 4, 5, 6, 7 and 8 CHARACTERIZED in that the applied film allows the free passage of copper ions through it, allowing it to act freely.
10. Producto biocida según reivindicaciones 1, 2, 3, 4, 5, 6, 7, 8 y 9 CARACTERIZADO porque el cobre a su vez sirve de estabilizante para las isotiazolinas. 10. Biocidal product according to claims 1, 2, 3, 4, 5, 6, 7, 8 and 9 CHARACTERIZED in that copper in turn serves as a stabilizer for isothiazolines.
11. Producto biocida según reivindicaciones 1, 2, 3, 4, 5, 6, 7, 8, 9 y 10 CARACTERIZADO porque su efectividad al inhibir la presencia de microorganismos, así como carencia de componentes tóxicos en su composición permiten su aplicación en la agroindustria, en especial en protectores de fruta, y en general para toda la industria alimenticia. 11. Biocidal product according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 CHARACTERIZED because its effectiveness in inhibiting the presence of microorganisms, as well as lack of toxic components in its composition allow its application in the agro-industry, especially in fruit protectors, and in general for the entire food industry.
PCT/CL2019/000023 2019-05-29 2019-05-29 Biocide product developed from isothiazolinones and nanoparticles of spherical copper WO2020237402A1 (en)

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