Pe or PVC coating material modified with metal-metal oxide nanoparticle

Abstract

The invention relates to the metal-metal oxide nanoparticle-modified PE or PVC plastic coating material, the relevant production and application method, which gives the iron wire and metal surface to where it is applied to antibacterial, antiviral, antifungal and self-cleaning properties due to its photocatalytic properties under light.

Description

[0001] PE or PVC coating material modified with metal-metal oxide nanoparticle

[0002] Field of the Invention

[0003] The invention relates to the metal-metal oxide nanoparticle-modified PE or PVC plastic coating material, the relevant production and application method, which gives the iron wire and metal surface to which it is applied antibacterial, antiviral, antifungal and self-cleaning properties due to its photocatalytic properties under light.

[0004] State of the Art

[0005] Contact of microbial species such as bacteria and viruses with abiotic surfaces leads to adhesion and binding events, followed by biofilm formation [1-3], Such contamination and cross-contamination incidents pose a major challenge and economic burden for the health care [4-6], food and food packaging [7-10], and water treatment industries [11, 12], For example, based on extensive research by the U.S. Centers for Disease Control and Prevention (CDC), healthcare-associated infections (HCAIs) are estimated to have a patient density of 4% in the United States

[0013] , A large proportion of these infections are associated with multi-purpose surgical instruments, medical implants, medical devices, and common surfaces in the healthcare setting [14-20], Similarly, according to CDC surveillance data, pathogenic microorganisms are estimated to cause 9.4 million cases of foodbome disease cases

[0021] ,

[0006] Nanotechnology offers great opportunities in various fields of science and technology. Pharmaceutical nanotechnology, which has many advantages, is increasingly becoming interesting to many researchers [2, 3], The application of nanomaterials in the fight against pathogens has been investigated for over two decades, with the novelty of dosage forms with improved therapeutic effects and physicochemical properties [4, 5], Various types and derivatives of nanoparticles are of great interest due to their potential antimicrobial effects.

[0007] The type of materials used to prepare the nanoparticles and the size of the nanoparticles obtained are two important parameters affecting the antimicrobial activity obtained [6, 7], In general, due to the fact that the surface to volume ratio of nanoparticles increases significantly with the reduction of particle size, nanoparticles have different properties compared to the same material with larger particles [8, 9], In fact, in nanometer sizes, the ratio of the surface molecule increases significantly, which leads to the improvement of some properties of the particles such as antimicrobial, mass transfer, dissolution rate and catalytic activity [8, 10], Although the exact mechanisms of the antibacterial effect of nanometals are still being investigated, there are two proposed mechanisms in this regard:

[0008] • Free metal ion toxicity due to dissolution of metals from the surface of nanoparticles,

[0009] • Oxidative stress formation by the formation of reactive oxygen species (ROS) on the surfaces of nanoparticles.

[0010] In addition, it has been proven that the morphological and physicochemical properties of nanometals have an effect on their antimicrobial activities [6, 12], Small nanoparticles are known to have the strongest bactericidal effect [8, 11, 13, 14], The positive surface charge of metal nanoparticles facilitates their binding to the negatively charged surface of bacteria, which can lead to increased bactericidal effect [6], The shape of the nanoparticles also affects their antimicrobial effects.

[0011] Among these, metal and metal oxide-based nanomaterials such as Ag [3], Cu, [4], CuO, ZnO [5], TiCh [6] and biopolymers containing graphene, chitosan nanoparticles [7, 8] are widely used in biomedical fields. These nanomaterials are non-toxic, biocompatible and can be easily synthesized using the biodegradable and easy solution technique. They also have antimicrobial properties [3-8], It is well known that nanomaterials offer a large number of active sites for antimicrobial reactions due to their large surface to volume ratios. When these nanomaterials are used for the production of a superhydrophobic coating, the developed nanocoating exhibits antimicrobial properties, often releasing metal ions or reactive oxygen species that effectively kill microorganisms (such as bacteria, fungi, and viruses). It should be noted that microbial growth needs moisture. Antimicrobial surfaces have wide application in medical textiles

[0014] , military garments [2], surgical instruments, bio-devices and biological anti-pollution coatings.

[0012] There are studies in the literature on the use of metal / metal oxide-based nanoparticles as antimicrobial agents. ZnO, a biocompatible material, is used as a suitable additive for textiles and surfaces in contact with its body

[0017] , ZnO nanoparticles showed bactericidal effect on Gram-positive and Gram-negative bacteria as well as spores resistant to high temperature and high pressure

[0018] , The enhanced antibacterial activity of ZnO nanoparticles compared to their microparticles is associated with the increased surface area in nanoparticles [6, 19, 20], Padmavathy et al. investigated the antibacterial activity of ZnO nanoparticles with various particle sizes. The results they obtained demonstrated that the bactericidal activity of ZnO nanoparticles increased by reducing the particle size

[0020] , Azam et al. They conducted a study in which the antimicrobial activity of ZnO, CuO and Fe2O3 nanoparticles against Gramnegative (E. coli and P. aeruginosa) and Gram-positive (S. aureus and Bacillus subtilis (B. subtilis)) bacteria were investigated comparatively. According to the results obtained, the highest bactericidal activity was obtained in ZnO nanoparticles, while Fe2O3 nanoparticles demonstrated the least antibacterial effect

[0018] , Particularly ZnO particles reduce bacterial viability; however, the exact mechanism of antibacterial activity is not yet fully understood. A suggested possibility is the formation of hydrogen peroxide as the main factor of antibacterial activity. It is believed that the accumulation of particles on the bacterial surface due to electrostatic forces may also be another mechanism of the antibacterial effect of ZnO particles

[0021] , In addition, ROS formed on the surface of particles, zinc ion release, membrane dysfunction and internalization of nanoparticles can also be considered as possible causes of cell damage

[0022] , In addition, it has been stated that transmembrane electron transport is interrupted in the case of some metal nanoparticles such as Ag, Cu and Zn.

[0013] Xie et al. They investigated the antibacterial activity of ZnO nanoparticles against Campylobacter jejuni (C. jejuni). They suggested that the antibacterial mechanism of ZnO nanoparticles may be due to cell membrane degradation and oxidative stress in C. jejuni. The results showed that ZnO nanoparticles caused morphological changes in C. jejuni and an increase in oxidative stress gene expression (up to 52 times)

[0019] , The antimicrobial property of TiO2 is related to its crystal structure, shape, and size

[0023] , It has been suggested that oxidative stress through the production of ROS may be a particularly important mechanism for TiO2 nanoparticles (forms of anatase). It was later found that ROS caused region specific DNA damage [24, 25], Roy et al. They investigated the effect of TiO2 nanoparticles with different antibiotics against methicillin resistant S. aureus (MRSA). They reported that TiO2 nanoparticles improved the antimicrobial effect of beta lactams, cephalosporins, aminoglycosides, glycopeptides, macrolides, lincosamides and tetracycline against MRSA. Another experiment showed that the antimicrobial resistance of MRSA to various antibiotics is reduced in the presence of TiO2 nanoparticles

[0025] , Haghhighi et al. They investigated the antifungal effect of TiCb nanoparticles on fungal biofilms (fluconazole resistant standard strains of Candida albicans (C. albicans)). According to the results obtained, the synthesized TiCb nanoparticles showed improved antifungal effect on fluconazole resistant strains of C. albicans biofilms. Researchers have suggested that TiCh nanoparticles can effectively inhibit fungal biofilms, especially those formed on the surface of medical devices

[0023] , The photocatalytic properties of TiCb nanoparticles help TiCb nanoparticles effectively destroy bacteria by producing ROS under UV light. Carre et al. suggest that antibacterial photocatalytic activity is accompanied by lipid peroxidation, which causes increasing membrane fluidity and disrupting cell integrity. However, the use of TiO2 nanoparticles under UV light has been restricted due to genetic damage to human cells and tissues [1], It has been proven that doping TiO2 nanoparticles with metal ions may be a good idea to overcome this problem. In addition, the antibacterial and photocatalytic properties ofTiO2 nanoparticles are significantly enhanced by doping with metal ions [1, 26], In other words, doping with metal ions shifts the light absorption range of TiCb nanoparticles to visible light, and therefore there is no need to be stimulated by UV light [1], Conjugation of TiCb nanoparticles with non-toxic polymers is another approach to overcome the toxicity problems of TiO2 nanoparticles. For example, Rafailovich et al. Reported that TiCb nanoparticles-polymer conjugates are harmless to fibroblast cells [1],

[0014] CaO and MgO indicate strong antibacterial activity related to alkalinity and active oxygen species. The antibacterial mechanism of CaO and MgO nanoparticles has been confirmed to provide an increase in pH with the formation of superoxide on the surface of these particles, as well as the hydration of CaO and MgO with water

[0027] , According to the studies, MgO nanoparticles damage the cell membrane and then cause leakage of intracellular content, which leads to the death of bacterial cells. Hewitt et al. It has been reported that MgO initiates susceptibility changes in E. coli induced by active oxygen

[0028] , However, Leung et al. Explains that the potent antibacterial activity of MgO nanoparticles can be observed in the absence of any ROS production. They reported that the mechanism of antimicrobial activity may be due to cell membrane damage

[0029] , MgO nanoparticles showed bactericidal activity against both Gram -positive and Gram -negative bacteria

[0030] , Sawai et al. Investigated the antibacterial activity of MgO against E. coli or S. aureus. They suggested that the presence of active oxygen, such as superoxide, on the surfaces of MgO nanoparticles is one of the primary factors affecting their antibacterial activity

[0031] , Jin and He also evaluated the antibacterial activities of MgO nanoparticles against E. coli and Salmonella Stanley, either alone or in combination with other antimicrobials (nisin and ZnO nanoparticles). MgO nanoparticles showed strong bactericidal activity against these pathogens (more than 7 log reduction in the number of bacteria). In their study, an increase in the antibacterial activity of MgO nanoparticles was observed as the MgO concentration increased. Researchers have suggested that MgO nanoparticles, by themselves or in combination with nisin, can be used as an effective antibacterial agent to improve food safety

[0032] , Jeong et al. Investigated the antimicrobial activity ofCaCO3 nanoparticles. According to the results obtained, CaCOs was converted into CaO as a result of heat treatment. CaO nanoparticles showed bactericidal activity against E. coli, S. typhimurium, S. aureus, and B. subtilis

[0033] ,

[0015] Yamamoto et al. Examined the antibacterial activity of CaCOs / MgO nanocomposites against Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria. According to the results, CaCCh / MgO nanocomposite shows more antibacterial effect against S. aureus than E. coli. The mechanism of the antibacterial action of CaO and MgO is due to the formation of superoxide on its surfaces, as well as the increase in pH by hydration of CaO and MgO with water

[0027] , Vidic et al. They evaluated the antimicrobial activity of the ZnO-MgO hybrid nanostructure. They also compared the antimicrobial activity of ZnO-MgO nanoparticles with pure ZnO and MgO nanoparticles. According to their findings, ZnO nanoparticles showed high antimicrobial activity against both Gram-positive (B. subtilis) and Gram-negative (E. coli). MgO nanoparticles showed moderate activity, while ZnO-MgO nanoparticles showed high antibacterial activity against Gram-positive bacteria. Microscopic analyses showed that B. subtilis cells were damaged after contact with ZnO-MgO nanoparticles. They suggested that nanostructured ZnO-MgO could be used as a safe new therapeutic for bacterial infections

[0030] ,

[0016] All the findings from the studies presented in the present art have shown that MgO and CaO nanoparticles show excellent antibacterial effect, either by themselves or in combination with other disinfectants. These nanoparticles are also low-cost, biocompatible and available materials. These properties make them promising antibacterial agents

[0029] , Researchers have suggested that these materials can be used in food processing and medical treatments as well as environmental protection

[0034] ,

[0017] Mahapatra et al. They tested the antibacterial activity of CuO nanoparticles against Klebsiella pneumoniae, P. aeruginosa, Salmonella paratyphi and Shigella strains. According to the results obtained, these nanoparticles showed appropriate antibacterial activity against the mentioned bacteria. The authors suggested that nanoparticles passing through the bacterial cell membrane and then damaging the vital enzymes of the bacteria are critical factors that trigger cell death. They also stated that these nanoparticles are not cytotoxic on the HeLa cell line

[0036] , Azam et al. They investigated the size dependent antibacterial activity of CuO nanoparticles. They investigated the antibacterial activities of CuO nanoparticles against two Gram-positive bacteria (S. aureus and B. subtilis) and two Gram-negative bacteria (Pseudomonas aeruginosa and E. coli). According to the results obtained, CuO nanoparticles showed inhibitory effect against both groups of the mentioned bacteria. The researchers concluded that the bactericidal activity of these nanoparticles depends on their size, stability, and concentration added to the growth medium. Researchers have stated that metal nanoparticles restrict bacterial growth by passing through nanometric pores located in the cell membrane of most bacteria

[0037] , Ahamed et al. investigated the antimicrobial effects of CuO nanoparticles (23 nm) against various bacterial strains (E. coli, P. aeruginosa, K. pneumoniae, Enterococcus faecalis, Shigella flexneri, S. typhimurium, Proteus vulgaris and S. aureus). Among these pathogens, E. coli and E. faecalis showed the highest susceptibility to CuO nanoparticles, while K. pneumoniae showed almost complete resistance to these nano formulations

[0035] ,

[0018] Currently, there is a need for studies to manufacture, characterize and study the antimicrobial properties of nanometal / metal oxide-based coating agents and to produce ready to use antimicrobial polymer based coatings by combining the antimicrobial properties of metal / metal oxide nanoparticles into a single formulation.

[0019] Consequently, due to the aforementioned negativities and deficiencies, there has been a need to make an innovation in the related technical field.

[0020] The Object of the Invention

[0021] The present invention relates to a metal-metal oxide nanoparticle modified PE or PVC coating material that meets the aforementioned requirements, eliminates all disadvantages and brings some additional advantages.

[0022] The object of the invention is to develop a PE or PVC plastic coating material modified with metal-metal oxide nanoparticle, which gives the applied iron wire and metal surface selfcleaning properties under light due to its antibacterial, antiviral, antifungal, photocatalytic properties. The object of the invention is to provide nanometal / metal oxide-based coating material with original formulations not found in the literature.

[0023] The object of the invention is to enable the production of merchandise made of wire coated with PE or PVC coating material modified with metal-metal oxide nanoparticle.

[0024] The object of the invention is to obtain a coating material with ready to use antimicrobial properties and self-cleaning under light.

[0025] The object of the invention is to provide a coating material that will enable microbial contaminants such as bacteria, viruses and fungi that may occur on the PE or PVC surface to be photocatalytically broken down and inactivated under antimicrobial and light conditions.

[0026] The object of the invention is to obtain a coating material that disrupts the structure of virus and bacterial DNA on the surfaces to which it is applied and makes these species inactive.

[0027] In order to fulfill the aforementioned objects, the invention is a material that gives the iron wire and metal surface to which it is applied the ability to self-clean under light due to its antibacterial, antiviral, antifungal, photocatalytic properties, characterized in that the said material is a PE or PVC coating material modified with metal (Ag, Cu, Zn)-metal oxide (TiCh, ZnO, CuO, MgO) nanoparticle in powder form.

[0028] PE or PVC coating material modified with metal-metal oxide nanoparticle to realize the objectives of the invention, comprises the following process steps:

[0029] • dissolving 10-1000 g of metal salt in distilled water to obtain metal oxide nanoparticles,

[0030] • adjusting the pH value of the obtained solution in the range of 10-12 with the addition ofNaOH,

[0031] • putting the obtained solution into a reaction by autoclaving it at 150 °C for 6-24 hours using a teflon autoclave.

[0032] • washing and drying the metal oxide nanoparticles obtained at the end of the reaction, • to obtain polymer coating material modified with metal-metal oxide nanoparticle; adding the synthesized nanoparticle into 1 kg PE or PVC plastic material with a utilization rate of 0.1-1% and mixing until a homogeneous mixture is obtained in the blowing chamber.

[0033] PE or PVC coating material modified with metal-metal oxide nanoparticle to realize the objectives of the invention, is applied with the following process steps,

[0034] • Homogeneous coating of the wire surface with the coating material by immersing the wire product heated to a temperature of 500 °C in the PE or PVC coating material modified with a homogenized metal-metal oxide nanoparticle,

[0035] • ensuring that the coating material is better adhered to the surface and dried by ironing the coated wires in the tunnel furnace at a temperature of 150°C,

[0036] The structural and characteristic features and all the advantages of the invention will be understood more clearly thanks to the detailed description given below, and therefore the evaluation should be made by taking this detailed description into consideration.

[0037] Detailed Description of the Invention

[0038] In this detailed description, the metal-metal oxide nanoparticle modified PE or PVC coating material is described for a better understanding of the subject only and in a way that does not have any limiting effect.

[0039] The invention relates to a metal-metal oxide nanoparticle-modified PE or PVC plastic coating material that provides antibacterial, antiviral, antifungal, self-cleaning properties to the iron wire and metal surface to which it is applied. The invention is characterized in that; it allows the production of wire products coated with metal (Ag, Cu, Zn)-metal oxide (TiCh, ZnO, CuO, MgO) nanoparticle modified PE or PVC plastic coating material. Thanks to the antimicrobial properties of metal-metal oxide nanoparticles and their function as photocatalysts under light, microbial contaminants such as bacteria, viruses and fungi that may form on the PE or PVC surface are inactivated. In addition, with the invention, due to the photocatalytic properties of metal (Ag, Cu, Zn)-metal oxide (TiCh, ZnO, CuO, MgO) nanoparticles as well as their antimicrobial properties, the virus and bacterial DNA structure on the surface is disrupted and these species are inactivated.

[0040] Within the scope of the invention, metal oxide nanoparticles were synthesized using the solvothermal method primarily. Subsequently, metal-metal oxide was used in the production of modified polymer coating materials.

[0041] Synthesis of metal oxide nanoparticles:

[0042] 10-1000 g from the salt of the relevant metal is taken and dissolved in pure water. The pH value of the obtained solution is adjusted to the range of 10-12 with the addition of NaOH. The obtained solution is put into a reaction by being autoclaved in the teflon autoclave at 150 °C for 6-24 hours. The metal oxide nanoparticles obtained at the end of the reaction are washed and dried.

[0043] Production of metal oxide modified polymer coating material:

[0044] 1 kg of PE or PVC plastic material will be taken and added to the PE or PVC plastic material as 0.1-1% of the synthesized nanoparticles, and the final metal oxide modified polymer coating material will be homogenized by mixing in a blowing chamber. The wire product heated to 500 °C will be immersed in homogenized metal-metal oxide modified PE or PVC plastic material and the wire surface will be coated homogeneously with the coating material. The coated wires will be kept in the tunnel furnace at a temperature of 150 °C to ensure better adhesion and drying of the coating material on the surface.

[0045] Within the scope of the invention, PE or PVC plastic coating material in powder form is produced, which provides photocatalytic properties to the iron wire and metal surface to which it is applied, thanks to its antibacterial, antiviral, antifungal, self-cleaning feature. The invention is characterized in that; it allows the production of wire products coated with metal (Ag, Cu, Zn)-metal oxide (TiCh, ZnO, CuO, MgO) nanoparticle modified PE or PVC plastic coating material. Thanks to the antimicrobial properties of metal-metal oxide nanoparticles and their function as photocatalysts under light, microbial contaminants such as bacteria, viruses and fungi that may form on the PE or PVC surface are inactivated. In addition, with the invention, due to the photocatalytic properties of metal (Ag, Cu, Zn)-metal oxide (TiCh, ZnO, CuO, MgO) nanoparticles as well as their antimicrobial properties, the virus and bacterial DNA structure on the surface is disrupted and these species are inactivated.

[0046] The antibacterial activity of the nanoantimicrobial agent was determined by the agar disc diffusion method. Bacterial strains: Escherichia coli (E.coli) (ATCC 25922) and Staphylococcus aureus (S. aureus) (ATCC 25923) are examples of the Gram-negative and Gram-positive bacterial class, respectively.

[0047] The inhibition zone was found to be 14.5±2.1 and 17.4±2 mm against E.coli and S. aureus, respectively.

[0048] Bovine coronavirus (BCoV); enveloped positive single stranded RNA virus and Bovine parainfluenza virus-3 (BPIV3) enveloped negative single stranded viruses were studied and their 1 and 24 hour antiviral performance was calculated with the equation below and given in the table.

[0049] Antiviral Performance (Mv= logEi- log )

[0050] Sample Contact Time

[0051] Ihour 24 hours

[0052] Nanoantimicrobial agent (BCV) 3.75 3.95

[0053] Nanoantimicrobial agent (BPIV3) 1.50 3.80

[0054] The photocatalytic properties of the prepared nanoantimicrobial agent were checked using methylene blue as the probe molecule. The degradation of methylene blue was carried out by exposing it to UV irradiation source at 380 nm wavelength. Analyses for methylene blue were performed by UV-Vis spectrophotometer at 664 nm, respectively. The results showed that REFERENCES

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Claims

CLAIMS1. A material that provides self-cleaning properties to the iron wire and metal surface to which it is applied due to its antibacterial, antiviral, antifungal and photocatalytic properties under light, characterized in that; said material is a PE or PVC coating material modified with metal (Ag, Cu, Zn)-metal oxide (TiCh, ZnO, CuO, MgO) nanoparticle in powder form.

2. Production method of the coating material according to claim 1, characterized in that; it comprises the following process steps:• dissolving 10-1000 g of metal salt in distilled water to obtain metal oxide nanoparticles,• adjusting the pH value of the obtained solution in the range of 10-12 with the addition ofNaOH,• putting the obtained solution into a reaction by autoclaving it at 150 °C for 6-24 hours using a teflon autoclave.• washing and drying the metal oxide nanoparticles obtained at the end of the reaction,• adding the synthesized nanoparticle into 1 kg PE or PVC plastic material to obtain polymer coating material modified with metal-metal oxide nanoparticle with a utilization rate of 0.1-1% and mixing until a homogeneous mixture is obtained in the blowing chamber.

3. Method of applying a metal-metal oxide nanoparticle modified PE or PVC coating material obtained by the production method according to claim 2, characterized in that; it comprises the following process steps:• homogeneous coating of the wire surface with the coating material by immersing the wire product heated to a temperature of 500 °C in homogeneous metal-metal oxide modified PE or PVC coating material,• ensuring that the coating material is better adhered to the surface and dried by ironing the coated wires in the tunnel furnace at a temperature of 150°C,

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