ES2331284A1 - Nanocompuestos materials with antimicrobial activity and the procedure for their obtaination (Machine-translation by Google Translate, not legally binding) - Google Patents

Abstract

Nanocomposite materials with antimicrobial activity and the procedure to obtain them. The present invention relates to new nanocomposite materials with antimicrobial activity, comprising a matrix and nanoadditives. Furthermore, the present invention describes a method for obtaining said nanocomposite materials and the use thereof in different sectors of the industry. (Machine-translation by Google Translate, not legally binding)

Description

Nanocomposite materials with activity antimicrobial and the procedure for obtaining it.

Technical Field of the Invention

The present invention relates to materials clay-based nanocomposites with antimicrobial activity. Such activity is obtained through the formulation of a type Specific nanoadditives based on natural clay sheets and / or synthetics that are interspersed with metals with capacity antimicrobial and / or salts thereof and / or with other compounds organic, inorganic or combination thereof.

In addition, the formulation of nanocomposite materials based on the incorporation of the aforementioned nanoadditives in a plastic matrix, or ceramic, by any method of manufacturing or processing plastics or preparation and is described. Ceramic powder processing. Thus, the nanoadditives are incorporated into plastic matrices by methods of deposition and evaporation of the solvent (eg coatings and lamination), application of the mon-American solution followed by polymerization and curing or cross-linking or vulcanication, operations typically used during the formulation of thermosets and elastomers, by melt mixing processes (eg extrusion, injection, blowing) and / or in-situ polymerization methods.

The nanocomposite materials with plastic matrix can be prepared by different procedures typically used in the processing and manufacturing of plastics, such as casting and / or rolling techniques (solvent dissolution and evaporation), melt mixing, thermosetting and elastomer formulation and of in-situ polymerization, for its advantageous application both in the packaging of products of interest for food and antimicrobial plastics, in surgical equipment, as well as for applications in other sectors.

In the case of nanocomposite materials with ceramic matrix, these are incorporated during the preparation of powders typically used in product manufacturing ceramics that involve grinding, atomization, pressing or extrusion, enamelling in the case of enameled products, and cooked.

In addition, the present invention relates to the use of said materials for multisectoral applications.

Background of the invention

In the field of polymers, one of the areas that is generating the greatest interest is the development of composite materials, and more specifically nanocomposites. There are different nanocomposite preparation techniques, both by the casting method ( Ogata N, Jimenez G, Kawai H, Ogihara T; J Polym Sci Part B: Polym Phys 1997; 35: 389-396, Chen GX, Hao GJ, Guo TY, Song MD, Zhang BH; J Appl Polym Sci 2004; 93: 655-61, Jimenez G, Ogata N, Kawai H, Ogihara T; J Appl Polym Sci 1997; 64: 2211-20 ), as per the method of melt mixed ( Sinha Ray S, Yamada K, Okamoto M, Ueda K. Nano Lett 2002; 2: 1093-6, MD Sanchez-Garcia, E. Gimenez and JM Lagaron (J. App. Pol. Sci., DOI 10.1002 / app), Di Y, lannace S, Maio ED, Nicolais L. J Polym Sci Part B: Polym Phys 2003; 41: 670-8 ) and by the in-situ polymerization method ( Messersmith PB, Giannelis EP. Chem Mater 1993; 5: 1064-6, Knani D, Gutman AL, Kohn DH. J Polym Sci. Part A: Polym Chem 1993; 31: 1221-32 ). In addition, these new nanocomposites and their processing techniques are described in US Patent Nos. 5747560; 4618528; 4528235; 4874728; 6391449; 6486253; 6376591 and 6156835; WO 95/14733; WO 93/04117 and more specifically with regard to the present invention in WO2007074184A1. In this PCT patent application, a new route for manufacturing nanocomposites that may or may not be biodegradable, with antimicrobial properties based on natural products and / or with controlled release capacity of other active or bioactive substances is described. These nanocomposites based on phyllosilicates and / or synthetic double laminar hydroxides are interspersed with different organic modifiers, and once incorporated into thermoplastic and / or thermostable matrices, they are able to improve the gas and vapor barrier properties. The aforementioned documents are some examples of patents and literature on nanocomposites of polymer-clay prepared from modified clays. These documents describe a nanocomposite material such as an exfoliated or interleaved plate, with a touch structure of nanometric dimensions, comprising intercalated clay dispersed in a polymer matrix, such as an oligomer, a polymer, or a mixture thereof.

For example, US 4739007 describes the nanocomposite preparation Nylon-6-clay from Montmorillonites treated with alkylammonium salts by the method of melt mixing.

Protection against the action of microorganisms is a basic requirement for many applications plastics, such as preserving the quality of packaged food, ensure aseptic conditions in Biomedical applications, contribute to limit the growth of microorganisms on exposed and work surfaces, among others Applications. Inventions related to the manufacture of antimicrobial systems for use in industry Textile, pharmaceutical and food. More specifically, patents US 6841244 and US 7232777 describe the manufacture of fibers with antimicrobial properties that contain silver. Patents KR20030038586, US 6224898 and US 7306777 refer to the use of nanocomposites of metallic silver and polyurethane, and metallic silver in dendrimeric polymers, respectively, with properties antimicrobial US Patents 7306777 and DE202005020859U describe the use of germicidal materials based on nanoparticles of silver applied in containers and packaging. Patent application 200703101 includes the manufacture of passive materials and packaging, (bio) active and intelligent with antibacterial properties by the incorporation of electro-stretched nanofibers containing silver nanoparticles However, so far it has not published any specific design in which the process is described of manufacturing nanocomposites for protection applications before the action of microorganisms.

The microorganisms, and specifically the bacteria, are the main cause of diseases caused by the Contaminated food consumption. These can survive the heat treatment required for canning or contaminating the food after such treatment due to sutures or leaks container. In addition to its potential health hazard, the Proliferation of microorganisms can cause alterations in the foods that in turn lead to changes in properties physical, chemical and organoleptic thereof. Some of the traditional preservation methods such as treatments thermal, irradiation, modified atmosphere packaging or addition of salts, cannot be applied to certain types of foods such as fresh vegetables, fruits and meats or ready-to-eat products.  Moreover, the direct application of antibacterial substances on food has limited effects since these are neutralize and diffuse rapidly into the food. Considering the above aspects, active packaging they constitute a viable and advantageous way to limit and control the bacterial growth in food, since the agents antimicrobials slowly migrate from the material to the surface of the product. The migration can be as extensive as required, from way that covers transport, storage and guaranteed time Until consumption. In the case of the antimicrobial nanoadditives of silver described in the present invention, once incorporated into containers can control microbial contamination by inactivation of the enzymatic metabolism of microorganisms.

The effect of microorganisms is also undesirable in other sectors. In the medical field, it is essential to eliminate the risks of infection in invasive treatments, of open wounds, as well as in routine treatments. As examples of such treatments, coatings with antimicrobial films of catheters and stethoscopes, and the preparation of fabrics in fibers pretreated with silver nitrate or with broad-spectrum antibiotics for wound and burn treatments can be cited. In the textile industry in terms of fashion and workwear, for example, the use of fibers pretreated with antibacterial agents limits the proliferation of microorganisms in the face of sweat, humidity and high temperatures, reducing bad body odors and risks of contagion. Fouling is the accumulation and deposition of biological material on surfaces exposed to various environmental conditions, such as boats, objects or painted systems exposed to high humidity conditions or other surfaces exposed to active, aggressive or environmentally adverse media. In the case of boats, fuel consumption can increase by up to 50% due to the hydrodynamic resistance offered by the accumulation of biological material in the hull. Antimicrobial systems can act as antifouling if they are applied in the form of layers on the surface of the boat, making fuel consumption optimal, and cleaning and maintenance operations less frequent. In the case of containers and water tanks, coating the interior with a film of antimicrobial compounds significantly reduces the growth of algae and the generation of bad odors, so that the quality of the water contained is guaranteed for longer. Coating with films of antimicrobial compounds or manufacturing with them the work surfaces of laboratories (clinical, microbiological, water analysis, food), of shops in which fresh food (butchers, fishmongers, etc.), of Hospital and health center pavilions, to mention just a few examples, guarantee adequate hygiene conditions for the development of work and eliminate the risk of contamination and infections. Plastic materials with antimicrobial properties can also be used in the manufacture of cranks, handlebars, handles and armrests of public transport elements, in railings and support points of places of high concurrence, in the manufacture of sanitary parts for public and mass use, as well as in headphones and microphones of telephones and audio systems of public places; kitchen tools and food transport, all this in order to reduce the risk of spreading infections and diseases. It is also of emerging interest to manufacture ceramic pieces that inhibit the proliferation of microorganisms on ceramic products, for example, the proliferation of fungi and molds on surfaces covered with ceramic tiles or on the junction points of these.

In the field of ceramic materials, there are patents describing the production of antibacterial ceramic compounds with Ag2W04 (silver wolfram) for use in sanitary parts (CN101062786); ceramic compounds with antimicrobial, fungicidal and deodorant properties containing dolomite and amphiphilic compounds (JP2007169109); vitreous and ceramic materials with silver incorporated as an antimicrobial agent (US2007172661, EP1711060); antimicrobial ceramics composed of mixtures of metal oxides (Ag 2 O, Fe 2 O 3, MnO 2, etc.) with which antimicrobial nanocomposites of low density polyethylene can be prepared for sheet use for food use (KR20010083418); antimicrobial vitreous ceramic compounds for dental applications (US2005142077). The previous examples show some of the applications of antimicrobial ceramic systems that eliminate or reduce the risk of spreading infections and contamination in potentially infectious environments (sanitary parts of public services, for example), in environments where microbial growth control is indispensable for the good development of activities (floor and wall tiles of operating rooms, clinical and toxicological laboratories, childcare centers, for example); in formulations for preparation and / or repair of mobile or fixed replacement dental parts (dentistry), among other applications
potential.

Description of the invention

As stated, so far it is not described the manufacture of nanocomposite materials with properties both barrier to gases and vapors, flame retardation, improved mechanical and thermal with respect to pure polymer, with the additional ability to block electromagnetic radiation (UV-Vis) and to allow fixing and / or controlled release of active and / or bioactive substances and that additionally have antimicrobial capacity due to the incorporation of nanoparticles of antimicrobial metals that confer sufficient thermal resistance to allow manufacture and processing of plastics and ceramic cooking.

However, and as seen above the PCT patent application (WO2007074184A1), is the most work close to that developed in the present invention, since describes the manufacture of nanocomposites with active properties (e.g. antimicrobial) and bioactive compounds based mainly of natural origin. The difference between this work and that of the present invention is that the properties antimicrobials are conferred or reinforced by incorporation of substances based on silver or other metals with capacity biocide in its structure. The incorporation of metal biocides in clays is not only interesting for the manufacture of nanocomposites based on the addition of such nanoadditives to plastics, but because the metal biocides resist heat treatments, which may also be necessary to favor the reduction of salts of biocidal metals to their corresponding metals can also be used in the ceramic industry for the manufacture of ceramic products and Porcelain with antimicrobial properties. Availability in The ceramic industry of antimicrobial nanoadditives allows increase the effectiveness of these products, due to the great dispersion that biocides exhibit in these matrices. Are obtained thus excellent results with lower proportions of nanoadditives, and therefore a significant reduction in costs.

The above examples allow define the field of application of the new materials nanocomposites with metal-based antimicrobial properties, whose procurement procedures are detailed herein patent. These nanocomposite materials antimicrobial metals prevent the development, growth and proliferation of microorganisms, as well as the spread of infections, in a wide variety of applications such as packaging (food, of drugs and medicines), in textile fibers and fabrics, in medical-surgical materials, in systems antifouling and manufacturing of plastic parts for sites public and for ceramic products.

Therefore the present invention relates to nanocomposite materials with antimicrobial activity, obtained by the introduction of laminar nanoadditives with or without previous modification of antimicrobial quaternary ammonium salts and / or chitosan and / or derivatives of this antimicrobial containing nanoparticles of metals and / or their organic and inorganic salts, in plastic or ceramic matrices, with advantageous application in the coatings, medicine, construction, textiles sectors anti-odor and container and packaging.

Consequently a first essential aspect of the The present invention relates to nanocomposite materials that they have plastic matrix, or ceramic and are constituted from the incorporation of lamellar-type clay nanoadditives.

Plastic matrices are selected without limiting sense of the group formed by thermoplastics, thermosets and elastomers such as polyolefins, polyesters, polyamides, polyimides, polyketones, polyisocyanates, polysulfones, styrenic plastics, phenolic resins, amide resins, resins ureas, melamine resins, polyester resins, resins epoxies, polycarbonates, polyvinylpyrrolidones, epoxy resins, polyacrylates, rubbers and rubbers, polyurethanes, silicones, aramids, polybutadiene, polyisoprenes, polyacrylonitriles, PVDF, PVA, PVOH, EVOH, PVC, PVDC or biomass derivatives and biodegradable materials such as proteins, polysaccharides, lipids and biopolyesters or mixtures of all these and may contain all kinds of additives typically added to plastics to improve their manufacturing and / or processed or its properties. In addition, said type of matrix is in a proportion from 5% to 99.99%; preferably from 20% up to 99.99%, and more preferably from 90% to 99.99%

Ceramic matrices understand and meaningless limiting, water, clays (preferably kaolinites and occasionally Montmorillonites), deflocculants, feldspars, feldspathic and occasionally sands, kaolin, carbonates and Zirconium The ceramic matrices of the enamel type and other type of ceramic coatings, include and without limitation kaolin or a kaolinitic clay (5%) or montmorillonite (1%), Feldspar, fried, silica and silica sands. In addition said type of matrix is in a proportion from 5% to 99.99%; preferably from 20% to 99.99%, and more preferably from 65% to 99.99%

According to a preferred embodiment, the matrices of plastic or ceramic type may contain agents with properties of barrier to electromagnetic radiation and fire resistance and other active or bioactive substances in addition to nanoadditives, selected from the group consisting of metal salts organic and inorganic antimicrobial (preferably silver, copper, nickel or cobalt), low molecular weight substances that have an active or bioactive character selected from ethanol, or ethylene, or of the essential oils type (preferably thymol, carvacrol, linalool and mixtures), or antimicrobial peptides of reduced size (preferably bacteriocins) natural or obtained by genetic modification (preferably nisins, enterocins, lacticins and lysozyme), or natural antioxidants or synthetic (preferably polyphenols, preferably flavonoids, rosemary extract or other plants and vitamins, preferably ascorbic acid or vitamin C), or drugs, or bioavailable enzymes or calcium compounds, or prebiotics (fiber not digestible).

The nanoadditives are selected from the group formed by laminar silicates and / or double laminar hydroxides. These above are selected without limitation of the group formed by montmorillonite, kaolinite, bentonite, clays smectite, hectorite, sepiolite, gibsite, dicktite, nacritite, saponite, halloisite, vermiculite, mica, and / or mixtures thereof or with other phyllosilicates, mainly, with or without modification previous organic and / or inorganic surface. These materials are characterized by being introduced as laminar type loads with sizes in the nanometer range at least the thickness of the particle, in plastic matrices and ceramic matrices for form the antimicrobial nanocomposites.

In plastic matrices, nanoadditives they are in a proportion from 0.01% to 95%, preferably from 0.01% to 80% and more preferably from 0.01 to 10%.

In ceramic matrices, nanoadditives they are in a proportion from 0.01 to 95%, by weight, preferably between 0.01% and 80% and more preferably from 0.01 to 35%.

In the ceramic matrices of the enamel type, the nanoadditives are in a proportion from 0.01% to 50%, preferably from 0.01% to 20% and more preferably from 0.01 to 15%.

The superficial modification of nanoadditives of clay when applied allows, in addition to introducing or accentuate antimicrobial activity, increase compatibility between the clay and the matrix to get better exfoliation of the clay. This is achieved, get a good morphology to improve the dispersion and surface exposure of an active substance antimicrobial, which are substances based on metals such as silver, copper, nickel, cobalt, iron, zinc and / or combinations of themselves and / or inorganic, organic salts, organic compounds, preferably salts allowed for food contact (that is that are included in the lists of monomers and others starting substances authorized by law to be used in the manufacture of materials and plastic objects) such as and without limiting sense hexadecyltrimethylammonium bromide, esters of polyethylene glycol with aliphatic monocarboxylic acids (C6-C22) and its sodium and ammonium sulfates, acid perfluorooctanoic acid and its ammonium salt, chloride copolymers N-methacryloxyxyethyl-N, N-dimethyl-N-carboxymethylammonium, chloride bis (2-hydroxyethyl) -2-hydroxypropyl-3- (dodecyloxy) methylammonium; and chitosan and its derivatives, and / or combinations thereof. The inorganic salts are selected from the group consisting of simple salts type nitrate, acetate, chloride, sulfate and inorganic complexes that include water and nitrates, acetate, amino and chloride groups.

In the case of plastic materials, they have antimicrobial activity and improvements in their barrier properties and other physical properties, resistance to fire and allow blocking of electromagnetic radiation, in addition to allowing the controlled release of substances with antioxidant and / or bioactive properties with respect to of pure material. In the case of ceramic materials, more effective antimicrobial properties are obtained due to the nanopar-
Ticulation

These nanocomposite materials are prepared in the case of plastics by means of lamination or coating techniques (casting of the solution), by application of the mon-American solution followed by polymerization and curing, operations typically used during the formulation of thermosets, by the above procedure but followed by crosslinking or vulcanizing, operations typically employed in the manufacture of elastomers, by melt mixing or in-situ polymerization.

In the case of their application in ceramics, these are incorporated and without limitation during the preparation of powders typically used in product manufacturing ceramics that involve grinding, atomization, pressing or extrusion, enamelling in the case of enameled and cooked products.

The plastic nanocomposite materials are of particular interest in the food packaging industry, since that these active containers allow to protect the product from the action of microorganisms and / or the controlled release of active substances and additionally, significantly improve the gas and vapor barrier properties, mechanical properties of UV barrier and others. In other fields of application, plastic and ceramic nanocomposite materials reinforced with nano-clays with antimicrobial properties are useful in the areas medical-surgical, biomedical and pharmaceutical, for the manufacture and coating of equipment and materials used in routine and invasive treatments. In applications "antifouling" to prevent the formation of biofilms in surfaces submerged and exposed to water and moisture, and in general, for all applications where a part is required, accessory and / or coating of antimicrobial compound to avoid the proliferation of microbes and risks of infections.

A second essential aspect of the present The invention relates to the process for manufacturing the nanocomposite materials described in the present invention, which they can be based on structures such as phyllosilicates lamellas, including clays (eg montmorillonite, kaolinite, bentonite, smectite, hectorite, sepiolite, saponite, halloisite, vermiculite, mica) or synthetic double laminar hydroxides or Natural laminar structure includes the following stages:

1) Decrease in particle size laminates by mechanical action for example by means of grinding technologies This process is carried out until obtaining a particle size below 30 microns in the D90.

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2) Classification in vibrotamiz, centrifugal, filtroprensa or any other filtration system via dry or wet to a range between 0.1 to 100 microns, preferably a decrease in particle size is achieved below 25 microns and more preferably below 3 microns in the so-called D90 (no more than 10% of the material is above of that value).

3) Elimination of organic matter by and without average limiting sense of decantation techniques, collection of supernatant or by chemical reaction with oxidizing substances such as peroxides

4) Elimination of crystalline oxides and hard particles not subject to modification well by processes centrifugation and / or gravimetric in solution or by turbo- dryers, preferably by a spin process well via wet or dry path followed or not by an atomization process with controlled depression or by any other drying process Industrial lyophilization included.

5) Obtaining fine laminar well in liquid suspension or by subsequent drying by the methods described in step 4) powder. These systems both in Liquid suspension as powder are considered as the product of the present invention.

6) Pre-treatment of laminar structures in one or several steps, by using precursors of the expander type as shown in Table 1.

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TABLE 1

one

2

Preferably the expanders are selected from the group consisting of DMSO, alcohols, acetates, or water and mixture of the above, and metallic salts of silver, copper, nickel or cobalt, which activate the fines by an initial increase in basal spacing of the sheets and modify the characteristics superficial clay. The penetration of precursors is will accelerate without limiting sense by using temperature, a turbulent, homogenizer, fluid homogenizer supercritical, pressure or mixture of the above. Drying These can be done by evaporation in an oven, freeze drying, centrifugation and / or gravimetric processes in solution or turbo-dryers or spray. According to another preferred embodiment of the present invention, the dissolution of the interleaved precursor may be used without a prior process of drying, as a starting medium for the next stage of incorporation of the modifier.

7) Additionally, or optionally, they can be intercalate in aqueous base or with polar solvents, substances inorganic, organic or hybrid in the laminar structure. In this same sense, the compounds to be inserted are selected and without limiting sense of the group formed by PVOH, EVOH and derivatives of the same family, and / or biopolymers such as peptides and proteins natural or synthetic via chemical or genetic modification of natural or synthetic microorganisms or plants and polysaccharides chemical pathway or genetic modification of microorganisms or plants and polypeptides, lipids, nucleic acids and acid polymers synthetic nuclei obtained via chemical or modification genetics of microorganisms or plants, and biodegradable polyesters such as polylactic acid, polylactic-glycolic, polycaprolactone, acid adipic and derivatives and polydroxyalkanoates, preferably polydroxybutyrate and its copolymers with valeriates, materials biomedical such as hydroxyapatites and phosphate salts organic. Quaternary ammonium salts can also be intercalated - preferably salts allowed for food contact (this is that they are included in the lists of monomers and others starting substances authorized by law to be used in the manufacture of materials and plastic objects) such as and without limiting sense hexadecyltrimethylammonium bromide, esters of polyethylene glycol with aliphatic monocarboxylic acids (C6-C22) and its sodium and ammonium sulfates, acid perfluorooctanoic acid and its ammonium salt, chloride copolymers N-methacryloxyxyethyl-N, N-dimethyl-N-carboxymethylammonium, chloride bis (2-hydroxyethyl) -2-hydroxypropyl-3- (dodecyloxy) methylammonium; and chitosan and its derivatives, and / or combinations thereof and more preferably hexadecyltrimethylammonium bromide -, silver, copper, nickel or its organic or inorganic salts, and other particles or nanoparticles with antimicrobial properties.

When the inorganic material that is sandwiched It is based on metals such as silver or organic salts and / or inorganic silver, copper, cobalt, nickel or other metals with antimicrobial power, a treatment can be applied later physical or chemical to change the oxidation state of the center interleaved metal, totally or partially. These treatments include no limitation: annealing at high temperatures (250-1200ºC), UV radiation, infrared radiation, microwave radiation, chemical reduction by ethanol and / or NaBH_ {4} and / or other chemical reducing agents. At the conclusion of any of these treatments will have modified the degree of oxidation of the metallic center, totally or partially, (silver, copper, nickel, zinc, cobalt, or other metal used), conferring on the material more or less intense antimicrobial properties.

When the organic material that is sandwiched is the EVOH or any material of the same family with contents ethylene molars preferably less than 48%, and more preferably under 29%, these are carried up to saturation in aqueous medium or in specific type solvents alcoholic and mixtures of alcohols and water, more preferably of water and isopropanol in proportions in volume of water greater than one fifty%.

On the other hand, biopolymers with or without plasticizers, with or without crosslinkers and with or without emulsifiers or surfactants or other nanoadditives, are from the group consisting of synthetic and natural polysaccharides (vegetable or animal) such as cellulose and derivatives, carrageenans and derivatives, alginates, dextran, gum arabic and preferably chitosan or any of its natural and synthetic derivatives, more preferably chitosan salts and even more preferably chitosan acetate, and both plant and animal derived proteins and corn proteins (zein), gluten derivatives, such as gluten or its gliadin and glutenin fractions and more preferably gelatin, casein and soy proteins and derivatives thereof, as well as natural or synthetic polypeptides preferably of the elastin type obtained by chemical or modification genetics of microorganisms or plants, lipids such as beeswax, car wax nauba, candelilla wax, shellac and fatty acids and monoglycerides and / or mixtures of all of the above.

In the case of chitosan the degree of deacetylation will preferably be greater than 80% and more preferably greater than 87%. The penetration of precursors will be accelerated by the use of temperature, a homogenizer of turbulent regime, ultrasound, pressure or mixture of previous.

In a later or alternative step to the dissolution of the pre-treated fines with precursors and modifiers previously proposed, will be added optionally low molecular weight substances that have active or bioactive character so that they are well interleaved or they are released in a controlled way giving rise to nanocomposites with active or bioactive capacity. The active substances will be ethanol, or ethylene, or of the essential oils type (preferably thymol, carvacrol, linalool and mixtures), or antimicrobial peptides of reduced size (preferably bacteriocins) natural or obtained by genetic modification (preferably nisins, enterocins, lacticins and lysozyme), or natural antioxidants or synthetic (preferably polyphenols, preferably flavonoids, rosemary extract or other plants and vitamins, preferably ascorbic acid or vitamin C), or drugs, or bioavailable enzymes or calcium compounds, or prebiotics (fiber non-digestible), or organic and inorganic metal salts (preferably silver, copper, nickel or cobalt). These elements are expected to be fixed for later release from the nanocomposite to the product so controlled (control of the matrix) and exercise their active role or bioactive, and / or that can be released from the matrix and that the nanoparticles control the kinetics (nanoadditive control). The contents to be added are generally less than 80% by volume of the solution, preferably less than 12% and more preferably less than 8%. The penetration of these substances will accelerate and without limiting sense by using of temperature, a homogenizer of turbulent regime, ultrasound, pressure or mixture of the above.

8) Add the result of the previous stages in solid or liquid state to a plastic or ceramic matrix. Alternatively, they can also be included on the matrix that Contains nanoadditives and additionally metal salts organic and inorganic antimicrobial (preferably silver, copper, nickel or cobalt) and / or any other type of substances active and bioactive without limiting sense of the above mentioned in order to reinforce or complement the effect active or bioactive nanocomposite. In the case of matrices plastics both nanoadditives and compounds Complementary mentioned above, can be added during processed using any manufacturing method related to The plastics processing industry such as extrusion, processes of application and curing typically used to manufacture and shape thermosetting and elastomers, injection, blowing, molding compression, resin transfer molding, calendering, shock thermal, ultrasonic internal mixing, co-extrusion, co-injection and mixing of these.

According to a preferred embodiment, the plastic matrix can be of any thermoplastic, thermoset or elastomer or of biomass derivatives and biodegradable materials such as proteins, polysaccharides, lipids and biopolyesters or mixtures of all of these and can contain all types of additives that improve the properties of barrier to electromagnetic radiation and fire resistance and / or other nanoadditives different from those described in this application and which are typically added to plastics to improve their processing or their properties. Alternatively, precipitation by evaporation of the resulting nanoadditives and modifiers set and, optionally, of the plastic matrix in solution can also be carried out, using drying methodologies such as heating and / or centrifugation and / or gravimetric processes in solution or turbo-dryers and / or atomization; by cooling or by adding a precipitating agent to form either a powder of the additive or a masterbatch or what is the same a concentrate of the nanoadditive in a plastic matrix.

In the case of the ceramic matrix, the salts organic and / or inorganic metals with antimicrobial properties can be added together with other active or bioactive substances at any stage of the manufacturing or processing of ceramic materials, although preferentially they will be added during the preparation of powders before atomization.

To matrix additive concentrates Polymeric can be treated in the following ways:

to)

be crushing to give rise to a product particulate by grinding.

b)

be process using any plastics processing methodology to obtain solid state pellets.

C)

be processes through any manufacturing process related to the  plastics processing industry such as extrusion, injection, blow molding, compression molding, resin transfer molding, calendering, thermal shock, internal mixing, ultrasound, coextrusion, coinjection and mixing of these.

d)

be used as an additive on any plastic matrix (including  biopolymers and biomedical materials cited) on a route Conventional plastics processing such as those mentioned in advance

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Finally, when the nanocomposite material It is reinforced with nanoadditives containing metals such as silver or organic and / or inorganic salts of silver, copper, cobalt, Nickel or other metals with antimicrobial power, can be applied, whether it has been done before or not, a physical treatment or chemical to change the oxidation state, totally or partially, of the metal center interspersed in the plastic or ceramic matrix well before, during or after conforming. These treatments include no limitation: annealing at high temperatures (250-1200ºC), UV radiation, infrared radiation, microwave radiation, chemical reduction by ethanol and / or NaBH_ {4} and / or other chemical reducing agents. At the conclusion of any of these treatments will have modified the degree of oxidation of the metallic center (silver, copper, nickel, zinc, cobalt, or other metal used), giving the material antimicrobial properties advantageous

Finally, a third essential aspect of the present invention relates to the use of nanocomposite materials obtained to reinforce antimicrobial activity in multisectoral applications in which it is required to limit microbial proliferation through the use of plastic materials and ceramic compounds, particularly in applications. of packaging and general packaging of food and food components (in the case of polymeric materials), in biomedical, medical-surgical and pharmaceutical applications, or in antifouling applications, in construction applications for enamels and tiles, in applications for cleaning products personnel and in contact applications in busy places such as supermarkets, carts, stands, linear, escalators or airports, in textile applications, such as gas barriers, vapors, solvents and organic products, such as aromas and components of aromas, oils, fats and hydrocarbons, already pr mixed organic and inorganic products, for applications that require biodegradable or compostable character, for active containers that require antimicrobial, antioxidant or other types that require controlled release of preferably low volatile molecular weight substances, for applications that require capacity antimicrobial and for the use of biopolymers either without the need to use plasticizing agents or in need of lower amounts of these.

Also these nanocomposite materials will serve as materials with radiation barrier properties Electromagnetic and fire resistance.

All the features and advantages exposed, as well as others of the invention, may be better understood With the following examples. On the other hand the examples that are show below, they are not limiting but illustrative so that the present can be better understood invention.

Brief description of the figures

The invention is described below with reference to the attached figures, in which:

Figure 1 corresponds to the diffractograms of X-rays (WAXS) obtained from a sample of Montmorillonite-type clay modified with bromide hexadecyltrimethylammonium (organic antimicrobial agent expanding and compatibilizing) and silver nitrate (temperature resistant antimicrobial), using ethanol as reducing agent by the method described in Example 1, and a Sample of the same type of unmodified clay. In this graph you observe how the antimicrobial system intercalates into the clay and shifts the natural clay peak towards lower angles.

Figure 2 is an image obtained by microscope transmission electronic (TEM) in which the main morphologies that can be observed in nanoloads obtained according to the present invention. The image corresponds to a aggregate of modified montmorillonite clay sheets with hexadecyltrimethylammonium bromide and silver nitrate, using ethanol as a reducing agent, by the method described in the Example 1. The formed silver nanoparticles can be observed on the surface.

Figure 3 corresponds to the diffractograms of X-rays (WAXS) obtained from a sample of kaolinitic clay (pretreated with DMSO) modified with hexadecyltrimethylammonium bromide (organic antimicrobial agent) expanding and compatibilizing) and with silver nitrate (temperature resistant antimicrobial), using UV radiation as a reducing agent by the method described in Example 2, and a sample of the same type of unmodified clay (pretreated with DMSO). This graph shows how the antimicrobial system is intersperses in the clay and as a result leads to disappearance of the peak of natural clay pretreated with DMSO.

Figure 4 is an image obtained by microscope transmission electronic (TEM) in which the main and typical morphologies that can be observed in the nanoloads obtained according to the present invention. The picture corresponds to an aggregate of kaolinitic clay sheets (pretreated with DMSO) modified with bromide hexadecyltrimethylammonium and silver nitrate, using UV radiation as  reducing agent, by the method described in Example 2.

Figure 5 is an image obtained by microscope electronic transmission (TEM) of an aggregate of sheets of Montmorillonite-type clay interspersed with silver nitrate, using ethanol as a reducing agent, by the method described in Example 3

Figure 6 is an image obtained by microscope electronic transmission (TEM) of an aggregate of sheets of kaolinitic clay (pretreated with DSMO) interspersed with silver nitrate, using UV radiation as a reducing agent, by the method described in Example 4.

Figure 7 corresponds to an image obtained by Transmission electron microscope (TEM) of a film obtained by casting nanocomposite of polylactic acid with 10% of kaolinite clay (pretreated with DSMO) interspersed with Silver nitrate, by the method described in Example 5.

Figure 8 shows the improvement in permeability to water vapor obtained in an acid nanocomposite film Polylactic with 10% kaolinite clay (pretreated with DMSO) interspersed with silver nitrate with respect to an acid film pure polylactic (Example 5).

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Examples Example 1

Synthesis and intercalation of nanoparticles of metallic silver in montmorillonite type clays modified with 33% by mass of hexadecyltrimethylammonium bromide, using ethanol as reducing agent. Initially the clay was dispersed already modified with 33% hexadecyltrimethylammonium bromide in ethanol, at ambient conditions, at a rate of 1 g of clay per 100 g of solvent, and 0.05 g of AgNO 3 was added to the dispersion. The dispersion was refluxed at 70 ° C for 6 hours; subsequently the dispersion was allowed to decant, the excess was removed of solvent and the clay was dried in a convection oven for 1 h at 70 ° C. The clay obtained was characterized using X-ray diffraction (see Figure 1) and microscopy transmission electronics (see Figure 2). The diffractograms of the Figure 1 demonstrate that modifying agents (particles of silver and hexadecyltrimethylammonium bromide) have been intercalated between the sheets, according to the displacement of the basal peak at angles lower (from 6.38 to 5.26). From the TEM images it was determined that in this case the silver nanoparticles reached between 3 and 23 nm, the average size being 16 nm; and that said nanoparticles they are presumably located in the interlaminar spaces of the clay, on the surface and edges.

In another study, the antimicrobial capacity of this clay with 5% silver nitrate against Salmonella spp . A pathogenic microorganism of food origin was used, such as Salmonella spp . CECT 554, which was obtained from the Spanish Type Culture Collection (Valencia, Spain). The study conditions were set in the use of the bacterium in the middle exponential phase and with an initial concentration of the microorganism of approximately 10 5 CFU / mL. The experimental part was carried out using an adaptation of the macrodilution method established for the determination of the bactericidal activity of antimicrobial agents approved in 1999 by the National Committee for Clinical Laboratory Standards. According to this method, 100 mg of the clay having a final silver concentration of 5% and 33% of hexadecyltrimethylammonium bromide was introduced into a sterile tube containing 10 mL of Mueller Hinton Broth (MHB) broth. Subsequently, and after 5 h, the tube was inoculated with 0.1 mL of a Salmonella spp . under the conditions described above. In parallel, two tubes containing sample without silver were inoculated (one with clay of the same type without any modification and another with clay of the same type modified with 33% hexadecyltrimethylammonium bromide), and another tube without sample that would serve as a control. Once the samples were inoculated, all tubes were incubated at 37 ° C for 24 hours. Then 0.1 mL of each sample were seeded in Triptona Soy Agar plates (TSA). After 24 hours of incubation at 37 ° C, viable cells were counted in the plate. Except for the control without sample and the control of clay without modification, a significant reduction in the number of viable was obtained after incubation at 37 ° C for 24 h (see Table 2). The control of modified clay with 33% hexadecyltrimethylammonium bromide shows a three-fold reduction in the number of viable after the incubation period, demonstrating that this modifying agent has some antibacterial activity. The clay sample modified with 5% silver nitrate and 33% hexadecyltrimethylammonium bromide reduced the number of viable by more than 99.9%, demonstrating the bactericidal capacity of this clay.

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TABLE 2

4

Example 2

Synthesis and intercalation of nanoparticles of metallic silver in kaolinite clays pretreated with dimethylsulfoxide (DMSO) and modified with 33% by mass of bromide hexadecyltrimethylammonium, using UV radiation as a reducing agent. Initially the kaolinite clay was pretreated with dimethylsulfoxide to increase interlaminar space. For it 60 g of clay was dispersed in 300 ml of dimethylsulfoxide, and kept under magnetic stirring and at 65 ° C for 24 h. Subsequently the clay was filtered by suction, washed with methanol and dried in a convection oven at 80 ° C for 6 hours.

Once dried, the clay pretreated with dimethylsulfoxide is dispersed in water, at a rate of 1 g of clay per 100 g of solvent, and then 0.05 g of AgNO 3 and 0.33 g of hexadecyltrimethylammonium bromide were added . The dispersion was maintained under vigorous and constant magnetic stirring under a source of UV radiation of 30 W and 235 nm wavelength. The exposure time to UV radiation was 24 h, then the solid was filtered by suction and dried in a convection oven at 70 ° C for 1 h. The clay obtained was characterized using X-ray diffraction (see Figure 3) and transmission electron microscopy (see Figure 4). The disappearance of the basal peak signal of kaolinite pretreated with dimethylsulfoxide and unmodified with hexadecyltrimethylammonium bromide in the diffractograms of Figure 3 (2 \ = 8.06), indicates that after simultaneous intercalation of hexadecyltrimethylammonium bromide and particles silver clays clays find steric impediments to be able to keep together. From the TEM images it was determined that in this case the silver nanoparticles reached between 3 and 24 nm, the average size being 10 nm; and that said nanoparticles are located on the surface, edges, and presumably, in the interlaminar spaces of the clay. In another study, the antimicrobial capacity of this clay with 5% silver nitrate against Salmonella spp . A pathogenic microorganism of food origin was used, such as Salmonella spp . CECT 554, which was obtained from the Spanish Type Culture Collection (Valencia, Spain). The study conditions were set in the use of the bacterium in the middle exponential phase and with an initial concentration of the microorganism of approximately 10 5 CFU / mL. The experimental part was carried out using an adaptation of the macrodilution method established for the determination of the bactericidal activity of antimicrobial agents approved in 1999 by the National Committee for Clinical Laboratory Standards. According to this method, 100 mg of the clay having a final concentration of 5% silver nitrate and 33% of hexadecyltrimethylammonium bromide was introduced into a sterile tube containing 10 mL of Mueller Hinton Broth (MHB) broth . Subsequently, and after 5 h, the tube was inoculated with 0.1 mL of a Salmonella spp . under the conditions described above. In parallel, two tubes containing sample without silver were inoculated (one with clay of the same type without any modification but pretreated with DSMO and another with clay of the same type pretreated with DMSO and modified with 33% of hexadecyltrimethylammonium bromide), and another tube without sample That would serve as control. Once the samples were inoculated, all tubes were incubated at 37 ° C for 24 hours. Then 0.1 mL of each sample were seeded in Triptona Soy Agar plates (TSA). After 24 hours of incubation at 37 ° C, viable cells were counted in the plate. Except for the control without sample and the control of clay pretreated with dimethylsulfoxide but without modification, a significant reduction in the number of viable (> 99.9%) was obtained, both in the control of clay pretreated with DMSO and modified with hexadecyltrimethylammonium bromide as in the clay sample pretreated with DMSO and modified with hexadecyltrimethylammonium bromide and silver nitrate after incubation at 37 ° C for 24 h (see Table 3). These results demonstrate that both hexadecyltrimethylammonium bromide and silver nanoparticles intercalated in kaolinite have a strong antimicrobial effect.

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TABLE 3

5

Example 3

Synthesis and intercalation of nanoparticles of metallic silver in unmodified montmorillonite clays, using ethanol as a reducing agent. Initially the ethanol clay, at ambient conditions, at a rate of 1 g of clay per 100 g of solvent, and 0.1 g of AgNO 3 was added to the dispersion This was refluxed at 70 ° C for 6 hours; subsequently the dispersion was allowed to decant, the excess was removed of solvent and the clay was dried in a convection oven for 1 h at 70 ° C. The clay obtained was characterized using diffraction  X-ray (see Figure 5). The diffractograms of Figure 5 indicate that there is no signal shift of the basal peak (6.38; 2)) after the incorporation of silver nanoparticles to the clay.

In another study, the antimicrobial capacity of this clay with 5% silver nitrate against Salmonella spp . A pathogenic microorganism of food origin was used, such as Salmonella spp . CECT 554, which was obtained from the Spanish Type Culture Collection (Valencia, Spain). The study conditions were set in the use of the bacterium in the middle exponential phase and with an initial concentration of the microorganism of approximately 10 5 CFU / mL. The experimental part was carried out using an adaptation of the macrodilution method established for the determination of the bactericidal activity of antimicrobial agents approved in 1999 by the National Committee for Clinical Laboratory Standards. According to this method, 100 mg of the clay having a final concentration of 5% silver nitrate was introduced into a sterile tube containing 10 mL of Mueller Hinton Broth (MHB) broth. Subsequently, and after 5 h, the tube was inoculated with 0.1 mL of a Salmonella spp . under the conditions described above. In parallel, a tube containing a sample without silver and another without a sample were inoculated, both would serve as controls. Once the samples were inoculated, all tubes were incubated at 37 ° C for 24 hours. Then 0.1 mL of each sample were seeded in Triptona Soy Agar plates (TSA). After 24 hours of incubation at 37 ° C, viable cells were counted in the plate. Except for both controls, a significant reduction in the number of viable (> 99.9%) was obtained after incubation at 37 ° C for 24 h (see Table 4).

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TABLE 4

6

Example 4

Synthesis and intercalation of nanoparticles of metallic silver in kaolinite clays pretreated with dimethylsulfoxide, using UV radiation as a reducing agent. Initially the kaolinite clay was pretreated with dimethylsulfoxide to increase interlaminar space. For it 60 g of clay was dispersed in 300 ml of dimethylsulfoxide, and kept under magnetic stirring and at 65 ° C for 24 h. Subsequently the clay was filtered by suction, washed with methanol and dried in a convection oven at 80 ° C for 6 hours.

Once dried, the pretreated clay with dimethylsulfoxide is dispersed in water at ambient conditions, at a rate of 1 g of clay per 100 g of solvent, and subsequently 0.05 g of AgNO 3 were added. The dispersion was maintained under vigorous and constant magnetic stirring under a source of UV radiation of 30 W and 235 nm wavelength. The exposure time to UV radiation was 24 h, after which the solid was filtered by suction and dried in a convection oven at 70 ° C for 1 h. The TEM image of Figure 6 shows an average size of reduced silver particles of 15 nm, and that these are found on the surfaces and edges of the clay sheets. In another study, the antimicrobial capacity of this clay pretreated with DMSO and modified with 5% silver nitrate against Salmonella spp . A pathogenic microorganism of food origin was used, such as Salmonella spp . CECT 554, which was obtained from the Spanish Type Culture Collection (Valencia, Spain). The study conditions were set in the use of the bacterium in the middle exponential phase and with an initial concentration of the microorganism of approximately 10 5 CFU / mL. The experimental part was carried out using an adaptation of the macrodilution method established for the determination of the bactericidal activity of antimicrobial agents approved in 1999 by the National Committee for Clinical Laboratory Standards. According to this method, 100 mg of the clay pretreated with DMSO was introduced which had a final concentration of 5% silver in a sterile tube containing 10 mL of Mueller Hinton Broth (MHB) broth. Subsequently, and after 5 h, the tube was inoculated with 0.1 mL of a Salmonella spp . in. the conditions described above. At the same time, a tube containing clay sample of the same type pretreated with dimethylsulfoxide but without silver and another without sample were inoculated, both would serve as controls. Once the samples were inoculated, all tubes were incubated at 37 ° C for 24 hours. Then 0.1 mL of each sample were seeded in Triptona Soy Agar plates (TSA). After 24 hours of incubation at 37 ° C, viable cells were counted in the plate. Except for the two controls, a significant reduction in the number of viable (> 99.9%) was obtained (see Table 5).

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TABLE 5

7

8

Example 5

Preparation of polylactic acid films with 10% kaolinite clay pretreated with dimethylsulfoxide and interspersed with silver nanoparticles. Initially, a 10% chloroform dispersion was prepared in weight (with respect to the dry polymer weight) of clay pretreated with dimethylsulfoxide and to which nanoparticles had been intercalated of silver under the UV reduction method. Subsequently the 5% polymer (polylactic acid) was added in weight in the dispersion of clay in chloroform. One was obtained silver polylactic acid / nano-clay nanocomposite film by solvent evaporation at ambient conditions, process called "casting." These nanocomposites were characterized studying its morphology by transmission electron microscopy (TEM, see Figure 7), as well as its vapor barrier properties of Water and antimicrobial. Additionally, permeability was studied to water (see Figure 8) of this polylactic acid film and 10% by weight of clay with antimicrobial properties, using the ASTM E96, at 25 ° C and 75% relative humidity. The adition of antimicrobial clay to the polymer matrix causes a reduction of permeability of 26.8%, so the composite It presents a better water barrier than pure polylactic acid.

To evaluate the antimicrobial capacity of the PLA films, 600 mg of film were weighed, both from the control without clay and from the sample with antimicrobial clay, and introduced into 10 mL of sterile culture medium. They were stored at 4 ° C for four weeks, prior to inoculation with Salmonella spp . Considering that the films contained 10% clay, and in turn that clay contained 5% silver nitrate, the final concentration of silver nitrate that has been used is 300 ppm, the minimum concentration being bactericidal (in this case, reduce the population to zero) of Salmonella around 100 ppm. The films contain an amount of silver 3 times higher than the bactericidal dose when used in suspension. After four weeks of storage and continued release, the controls show an increase in the number of viable three orders of magnitude, while in the sample of PLA film with 10% clay interspersed with silver the viable three orders of reduction are reduced. magnitude (see
Table 6).

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TABLE 6

9

Example 6

Preparation of chitosan films with 10% kaolinite clay pretreated with dimethylsulfoxide and interspersed with silver nanoparticles. Initially, a 0.9% solution of chitosan in 1% acetic acid is prepared at 70 ° C. This solution was filtered and a 10% by weight dispersion in water (with respect to the polymer dry weight) of kaolinite clay pretreated with dimethylsulfoxide and interspersed with silver nanoparticles was added under vigorous stirring. It is poured into Petri dishes and the solvent is allowed to evaporate at ambient conditions. A chitosan / nano-clay silver nanocomposite film was obtained by the process called "casting". To evaluate the antimicrobial capacity of chitosan films, different portions of films were weighed and stored at 4 ° C for 12 hours before inoculation with Salmonella spp . The weights used were: 25, 50 and 75 mg of film, which were placed in 10 mL tubes with sterile culture medium. The chitosan films contained 10% clay, which in turn contained 5% silver, so the final concentrations of silver nitrate used are the following: 25 mg of chitosan film contained 0.125 mg of silver nitrate ; 50 mg of film contained 0.25 mg of silver; and 75 mg of film contained 0.375 mg of silver. The results in Table 7 show that chitosan control films (without clay) have some antimicrobial activity, since as the weight of the film increases, the number of viable bacteria decreases, with 75 mg of film sufficient to totally inhibit Bacterial growth in the medium at the given conditions. Samples with 10% clay have greater capacity to inhibit growth, with 25 mg of film the number of viable is reduced by three orders of magnitude and from 50 mg of film total growth inhibition is obtained.

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TABLE 7

10

Example 7

Evaluation of the antimicrobial capacity of PVOH and EVOH films with 10% pretreated kaolinite clay with dimethylsulfoxide and interspersed with silver nanoparticles. TO 5% solutions of PVOH and EVOH were uniformly incorporated into 10% (based on polymer weight) of kaolinite clay pretreated with dimethylsulfoxide and interspersed with nanoparticles silver. Subsequently the respective films were obtained by evaporation of the solvent (casting process) and stored in a  desiccator at 0% relative humidity and at room temperature.

For the evaluation of the antimicrobial capacity, 100 mg of each of the films obtained in 10 mL of sterile culture broth were introduced and stored at 4 ° C for 72 hours before inoculation with Salmonella spp . In parallel, control tubes without sample and control films of PVOH and EVOH without clays were prepared. A set of samples and controls was also prepared under the same conditions that were immediately processed, in order to study the release of the antimicrobial agent from the matrices with respect to time. The results in Table 8 show that control films without clays allow multiplication of the number of viable up to two orders of magnitude, regardless of storage time. EVOH film samples with 10% clay interspersed with silver nitrate reduced 100 times the number of viable at the time of inoculation and then, 100 times more after 72 hours of incubation. On the other hand, samples of PVOH films with 10% silver clay showed a reduction of four orders of magnitude of the number of viable at the time of inoculation of the sample and total inhibition after 72 hours of incubation. These results show the bactericidal activity of clays intercalated with silver incorporated in matrices of EVOH and PVOH, being the most pronounced antimicrobial effect in the latter polymer.

TABLE 8

eleven

Claims (32)

1. Nanocomposite materials with antimicrobial activity, characterized in that they comprise the following elements:

to.

matrix;

b.

nanoadditives

2. Nanocomposite materials with antimicrobial activity according to claim 1, characterized in that the matrix is plastic or ceramic. 3. Nanocomposite materials with antimicrobial activity according to claim 2, characterized in that the plastic matrix is selected without limitation from the group formed by the families of thermoplastics, thermosets, elastomers and materials derived from biomass and / or biodegradable or mixtures thereof containing additives typical that are added during the manufacture and processing of plastics and bioplastics. 4. Nanocomposite materials with antimicrobial activity according to claim 2, characterized in that the plastic matrix is in a proportion from 5% to 99.99%; preferably from 20% to 99.99%, and more preferably from 90% to 99.99%. 5. Nanocomposite materials with antimicrobial activity according to claim 2, characterized in that the ceramic matrix comprises at least the following elements:

to.

Water;

b.

clays;

C.

deflocculants;

d.

feldspar;

and.

feldspathic sands; Y

F.

kaolin, carbonates and zirconium.

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6. Nanocomposite materials with antimicrobial activity according to claim 2, characterized in that the ceramic matrix when it is of enamel type comprises at least the following elements:

to.

kaolin or a kaolinitic clay or montmorillonitic;

b.

feldspar;

C.

fried

d.

silica; Y

and.

silica sands.

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7. Nanocomposite materials with antimicrobial activity according to claim 2, characterized in that the ceramic matrix is in a proportion from 5 to 99.99%, preferably from 20 to 99.99%, and more preferably from 65 to 99.99 %. 8. Nanocomposite materials with antimicrobial activity according to claim 2, characterized in that the ceramic matrix when it is of enamel type comprises at least the following elements:

to.

kaolin or a kaolinitic clay or montmorillonitic,

b.

feldspar;

C.

fried

d.

silica; Y

and.

silica sands.

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9. Nanocomposite materials with antimicrobial activity according to claim 1, characterized in that the matrix contains agents with electromagnetic radiation barrier properties, fire resistance and / or active and / or bioactive substances selected from the group consisting of organic and inorganic metal salts antimicrobials and / or substances of low molecular weight with active or bioactive character. 10. Nanocomposite materials with antimicrobial activity according to claim 1, characterized in that the nanoadditives are of the laminar type with or without prior modification containing at least one active agent with antimicrobial activity. 11. Nanocomposite materials with antimicrobial activity according to claim 10, characterized in that the laminar-type nanoadditives are based on synthetic double-layered phyllosilicates and / or laminar structure hydroxides. 12. Nanocomposite materials with antimicrobial activity according to claim 1, characterized in that the nanoadditives are in a proportion from 0.01 to 95%, preferably from 0.01 to 80% and more preferably from 0.01 to 10% if The matrix is plastic type. 13. Nanocomposite materials with antimicrobial activity according to claim 1, characterized in that the nanoadditives are in a proportion from 0.01 to 95%, preferably from 0.01 to 45% and more preferably from 0.01 to 35% if The matrix is ceramic type. 14. Nanocomposite materials with antimicrobial activity according to claim 1, characterized in that the nanoadditives are in a proportion from 0.01 to 50%, preferably from 0.01 to 20% and more preferably from 0.01 to 15% if The ceramic matrix is enamel type. 15. Nanocomposite materials with antimicrobial activity according to claim 10, characterized in that the active agent with antimicrobial activity is selected from the group consisting of metals and / or their organic and inorganic salts, organic compounds, and / or combination thereof. 16. Nanocomposite materials with antimicrobial activity according to claim 15, characterized in that the metals are selected from the group consisting of silver, copper, nickel, cobalt, iron, zinc or a combination thereof. 17. Nanocomposite materials with antimicrobial activity according to claim 15, characterized in that the organic compounds are selected from the group consisting of quaternary ammonium salts, preferably hexadecyltrimethylammonium bromide, polyethylene glycol esters with monocarboxylic aliphatic acids (C6-C22) and their ammonium sulfates and sodium, perfluorooctanoic acid and its arnonium salt, copolymers of N-methacryloxyethyl-N, N-dimethyl-N-carboxymethyl ammonium chloride, bis (2-hydroxyethyl) -2-hydroxypropyl-3- (dodecyloxy) methylammonium chloride; and chitosan and its derivatives, and / or combinations thereof. 18. Nanocomposite materials with antimicrobial activity according to claim 15, characterized by the inorganic compounds are selected from the group consisting of simple salts such as nitrate, acetate, chloride, sulfate and inorganic complexes that include water and the nitrate, acetate, amino and chloride groups. 19. Method for obtaining nanocomposite materials with antimicrobial activity according to claims 1 to 18, characterized in that it comprises the following steps:

to.

decrease in size nanoadditives by mechanical action;

b.

dry or wet filtration of the particles obtained in the previous stage;

C.

elimination of organic matter, crystalline oxides and hard particles not subject to modification until obtaining laminar structures;

d.

pre-treatment of laminar structures by means of precursors;

and.

addition to a plastic matrix or ceramics.

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20. Procedure for obtaining nanocomposite materials with antimicrobial activity according to claim 19, characterized in that the decrease in the size of the nanoadditives is carried out up to particle sizes below 30 microns in D90. 21. Method according to claim 19, characterized in that the filtration is carried out up to a particle size from 0.1 to 100 microns, preferably below 25 microns and more preferably below 3 microns in the D90.

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22. Method according to claim 19, characterized in that the elimination of organic matter is done by decanting techniques, supernatant collection or by chemical reaction with oxidizing substances. 23. Method according to claim 19, characterized in that the elimination of crystalline oxides and hard particles not subject to modification is carried out by centrifugation and / or gravimetric processes in solution or by turbo-dryers. 24. Method according to claim 19, characterized in that the precursors are of the expander and / or compatibilizer and / or antimicrobial type. 25. Method according to claim 19, characterized in that after the pre-treatment stage of the laminar structures by means of precursors, a drying step is carried out. 26. Method according to claim 19, characterized in that after the pre-treatment stage of the laminar structures by means of precursors, an intercalation stage with modifiers is carried out. 27. Method according to claim 26, characterized in that after intercalating a step of adding low molecular weight substances with active and / or bioactive character is carried out. 28. Method according to claim 27, characterized in that after the step of adding low molecular weight substances a precipitation step is carried out by evaporation, centrifugation, cooling or addition of precipitating agents. 29. Method according to claim 19, characterized in that in the step of adding to a plastic or ceramic matrix an incorporation of antimicrobial metal or inorganic salts is carried out. 30. Method according to claim 19, characterized in that after the step of adding the matrix, a physical or chemical treatment is carried out to change the oxidation state, totally or partially, of the metal center intercalated in the matrix. 31. A method according to claim 26, characterized in that the modifiers are selected from the group consisting of inorganic, organic substances, including materials derived from biomass and / or biodegradable and / or salts or other antimicrobial compounds. 32. Use of nanocomposite materials with antimicrobial activity of claims 1 to 18, for food and food component packaging and packaging applications, in biomedical, medical-surgical and pharmaceutical applications, in antifouling applications, in construction applications for enamels and tiles, in applications for personal care products and in contact applications in busy places such as supermarkets, carts, stands, linear, escalators, or airports, in textile applications, in applications that require a gas barrier, vapors and solvents and organic products, such as aromas and components of aromas, oils, fats and hydrocarbons, and mixed organic and inorganic products, for applications that require biodegradable or compostable character, for active packages that require antimicrobial, antioxidant or other types that require controlled release of substance Low molecular weight preferably volatile, for applications that require antimicrobial capacity, for the use of biopolymers either without the need for use of plasticizing agents or requiring lower amounts of these and as materials with electromagnetic radiation barrier properties and Fire resistance.