KR20230133011A - Antibacterial or Antivirus Coating Composition Comprising Inorganic Nanoparticles with High Transparency and Film Using Same - Google Patents

Abstract

The present invention relates to a highly transparent antibacterial or antiviral coating composition containing inorganic nanoparticles and a film using the same.
The antibacterial or antiviral coating composition according to the present invention has excellent dispersibility and adhesion, can control coating performance by adjusting the properties of ingredients, has excellent process convenience, and can easily form a thin film. In addition, when an antibacterial or antiviral film is manufactured using the coating composition of the present invention, interfacial peeling occurring in the multilayer structure of the film is prevented, transparency is excellent, antibacterial or antiviral properties are excellent, and a flexible film can be manufactured. .

Description

Highly transparent antibacterial or antiviral coating composition containing inorganic nanoparticles and film using the same {Antibacterial or Antivirus Coating Composition Comprising Inorganic Nanoparticles with High Transparency and Film Using Same}

The present invention relates to a highly transparent antibacterial or antiviral coating composition containing inorganic nanoparticles and a film using the same.

Quarantine refers to measures taken against the source and route of infection to prevent the spread of infectious diseases. Since the spread of the coronavirus, the spread of infection centered on droplets has been recognized as a very big social problem. In everyday life, when droplets are transferred to various surfaces, they can be transmitted to the stage of contagion, expanding the route of non-contact infection. This issue is a factor that causes people to withdraw from social activities and causes tension during daily life, thereby reducing the quality of life. It acts as However, since the droplets themselves cannot be prevented, it is important to deal with the bacteria or viruses carried by the droplets. In other words, if bacteria or viruses can be removed when they reach a specific surface, the problem of infection caused by droplets can be solved.

Controlling the wettability of the surface is very important in order to effectively remove bacteria or viruses present in droplets from the surface. For this purpose, two approaches are generally proposed. One is to use a super water-repellent coating to make contact with droplets completely impossible. In this case, very effective protection is possible on the coating surface, but droplets may continue to float. Conversely, a method can be used to impart superhydrophilicity to the surface to induce droplets to quickly contact and react quickly with a specific mechanism of the surface.

In this way, a composite film process is required to impart superhydrophobic or superhydrophilic properties to the surface and control performance. Composite film is a product technology with a multi-layer structure, which allows the flexibility and durability of the product to be easily adjusted and provides various functionalities at the same time. Control of antiviral properties and surface wettability can be carried out using various methods and materials depending on the case, so a composite film forming process is essential for this.

However, most current products remain at the level of using general copper particles or zinc oxide, as disclosed in Republic of Korea Patent Publication No. 10-2021-0151576, and no specific measures for improving functionality are provided. Accordingly, there is a need for the development of long-term sustainable technologies that can improve functionality and convenience for consumers while having excellent antibacterial or antiviral properties.

The purpose of the present invention is to provide an antibacterial or antiviral coating composition that has excellent dispersibility and adhesion, is easy to form a thin film, and has excellent processability.

Another object of the present invention is to provide an antibacterial or antiviral film with excellent antibacterial or antiviral properties and suppressed interfacial peeling.

In order to achieve the above-described object, the present invention provides a coating composition containing inorganic nanoparticles and polymers.

In the present invention, the polymer may be a copolymer prepared using an acrylate-based monomer.

In the present invention, the polymer may include one or more binder polymers selected from acrylic polymers and urethane polymers.

In the present invention, the polymer may include one or more functional groups selected from the group consisting of an alkyl group, an aryl group, a carboxyl group, a hydroxy group, a thiol group, and an isocyanate group in the molecule.

In the present invention, the polymer may be manufactured using a binder precursor containing a backbone compatible with the filler, a photocurable functional group, and a ring-opening thermosetting functional group.

In the present invention, the inorganic nanoparticles may include one or more types selected from the group consisting of single-structured metal nanoparticles, composite metal nanoparticles, and metal ceramic composite particles.

In the present invention, the inorganic nanoparticles may include one or more metal components selected from the group consisting of copper, gold, silver, and zinc.

In the present invention, the inorganic nanoparticles may be processed using an electron beam.

The present invention also provides an antibacterial or antiviral film including a coating layer formed by coating the coating composition.

In the present invention, gravure coating, slot die coating, Mayer bar coating, doctor blade, etc. may be used as the coating method.

In the present invention, the film is prepared by applying the coating composition; Photocuring the applied composition; and heat curing.

In the present invention, the film may be hydrophilic or water-repellent.

The antibacterial or antiviral coating composition according to the present invention has excellent dispersibility and adhesion, can control coating performance by adjusting the properties of ingredients, has excellent process convenience, and can easily form a thin film. In addition, when an antibacterial or antiviral film is manufactured using the coating composition of the present invention, interfacial peeling occurring in the multilayer structure of the film is prevented, transparency is excellent, antibacterial or antiviral properties are excellent, and a flexible film can be manufactured. .

Figure 1 schematically shows the control of particle dispersibility according to the application of a dispersant in a coating composition.
Figure 2 relates to a synthesis process of a polymer with an acrylate-based multifunctional structure according to an exemplary embodiment of the present invention.
Figure 3 schematically shows the polymer structure design according to an exemplary embodiment of the present invention.
Figure 4 shows a method of forming a system using a polymer according to an exemplary embodiment of the present invention.
Figure 5 shows a method of forming a polymer crosslinking system according to an exemplary embodiment of the present invention.
Figure 6 shows a coating formation process using a binder precursor according to an exemplary embodiment of the present invention.
Figure 7 schematically shows the structure of metal ceramic composite particles used in an exemplary embodiment of the present invention.
Figure 8 shows inorganic particles prepared according to an exemplary embodiment of the present invention.
Figure 9 schematically shows an electron beam particle manufacturing process according to an exemplary embodiment of the present invention.
Figure 10 schematically shows how bacteria or viruses are transmitted to a surface through moisture such as droplets.
Figure 11 shows the relationship between surface energy control and change in wettability properties.
Figure 12 schematically shows the equipment and coating method used in the film coating process according to an exemplary embodiment of the present invention.
Figure 13 shows a coating apparatus used in an exemplary embodiment of the present invention.
Figure 14 shows the structure of a coating roll used in an exemplary embodiment of the present invention.
Figure 15 is a diagram showing that each layer exhibits different characteristics in a multi-layered film.
Figure 16 is a photograph of interfacial peeling occurring in a film with a multilayer structure.
Figure 17 shows a photograph of an antibacterial activity test of a coating composition according to an embodiment of the present invention.
Figure 18 shows a surface photograph of a coating film manufactured by applying composite particles according to an embodiment of the present invention.
Figure 19 shows the results of durability measurement of a material manufactured by applying composite particles according to an embodiment of the present invention.
Figure 20 shows the results of measuring antibacterial/antiviral properties of a surface manufactured by applying composite particles according to an embodiment of the present invention.

Hereinafter, specific implementation forms of the present invention will be described in more detail. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

The present invention relates to a highly transparent antibacterial or antiviral coating composition containing inorganic nanoparticles and a composite film using the same.

The antibacterial or antiviral coating composition according to the present invention has excellent dispersibility and adhesion, can control coating performance by adjusting the properties of ingredients, has excellent process convenience, and can easily form a thin film. In addition, when an antibacterial or antiviral film is manufactured using the coating composition of the present invention, interfacial peeling that occurs in a multilayer structure is prevented, transparency is excellent, antibacterial or antiviral properties are excellent, and a flexible film can be manufactured.

In the present invention, the coating composition may include inorganic nanoparticles and polymers.

In the present invention, the polymer may be a copolymer prepared using an acrylate-based monomer.

In the case of existing antibacterial/antiviral coatings or films, simultaneous dispersion is difficult when fillers are complex or the number of types increases, so a method to improve dispersibility is needed. Figure 1 schematically shows the control of the dispersibility of particles according to the application of a dispersant. In the present invention, the dispersion and dispersion of particles is controlled by controlling the acrylate copolymer manufacturing process to maximize compatibility with various fillers and strengthen adhesive properties. It is possible to provide a material that can satisfy both adhesion characteristics.

Figure 2 relates to a synthesis process of a polymer having an acrylate-based multifunctional structure according to an exemplary embodiment of the present invention. According to this polymer structure design, a multicomponent polymerization process, polymerization scale-up and Particle bonding can be optimized.

The binder polymer used in the present invention may include one or more of an acrylic polymer and a urethane polymer.

In the present invention, the binder polymer may include one or more functional groups selected from the group consisting of an alkyl group, an aryl group, a carboxyl group, a hydroxy group, a thiol group, and an isocyanate group in the molecule. Figure 3 schematically shows the polymer structure design according to an embodiment of the present invention.

In the present invention, the core first method, coupling onto method, or arm first method can be used as a method of forming a system using a polymer, as shown in FIG. 4. In addition, the method of forming a cross-linked system of a polymer according to the present invention includes the steps of manufacturing a cross-linked polymer as shown in Figure 5, manufacturing a comb polymer by controlling the branches, and manufacturing a star polymer based on manufacturing an arm polymer. And it may include one or more steps of preparing a photocurable hybrid-star polymer by controlling the functional group.

In the present invention, the binder polymer can be manufactured using a binder precursor containing a backbone compatible with the filler, a photocurable functional group, and a ring-opening thermosetting functional group, and the binder precursor may have low viscosity characteristics.

Figure 6 schematically shows an example of a coating formation process using a binder precursor according to the present invention. The antibacterial or antiviral film of the present invention includes the steps of applying the coating composition of the present invention; photocuring the composition; and heat curing.

According to the present invention, the content of filler in the coating can be maximized, and the viscosity can be controlled according to the skeletal structure (length) of the binder precursor. In addition, by using a binder containing hydroxy groups, carboxyl groups, thiol groups, etc., compatibility with fillers can be improved and dispersion performance can be maximized. Additionally, the shadow curing problem of photocuring can be solved using a thermal curing process, and the shrinkage problem that occurs during curing can be solved using a ring-opening reaction.

In the present invention, the inorganic nanoparticles may include one or more types selected from the group consisting of single-structured metal nanoparticles, composite metal nanoparticles, and metal ceramic composite particles. The inorganic nanoparticles may contain one or more metal components selected from the group consisting of copper, gold, silver, and zinc. Figure 7 shows an example of the metal ceramic composite particles.

In the present invention, the inorganic particles may be processed using an electron beam.

In the present invention, by selectively manufacturing nano/micro particles through electron beam processing, it is possible to provide a technology that complements the functional properties of existing particles while being highly economical and capable of large-scale mass production.

Figure 8 shows inorganic particles manufactured according to an embodiment of the present invention, and Figure 9 schematically shows the electron beam particle manufacturing process according to an embodiment of the present invention. Generally, metal-based nanoparticles use a precursor. It is manufactured through chemical processing, but in the present invention, the precursor is quickly converted into particles through an electron beam process, the shape of the particle and various performances are realized through property control, and functional particles can be manufactured through the use of a composite precursor. .

In addition, in the present invention, in order to effectively remove bacteria or viruses that are transmitted through moisture like droplets, that is, dissolved in liquid substances, as shown in Figure 10, a composite that can distinguish between the part that controls wettability and antibacterial or antiviral properties A surface that demonstrates performance was created. Performance was improved by introducing a hybrid coating method to areas that exhibit wettability, and the area was minimized to maximize antibacterial or antiviral performance.

In addition, the coating composition of the present invention may further include additives such as surfactants, dispersants, and photocatalysts.

In one embodiment of the present invention, by using a system such as a hydrophilic surfactant, it is possible to enhance moisture wettability, propose a structure capable of binding, and use superhydrophilic technology to ensure durability. In another embodiment of the present invention, a new process can be designed to implement water-repellent properties to lower surface energy and break down or disrupt the antiviral structure by excellent adhesion. Figure 11 shows the relationship between surface energy control and change in wettability properties.

In the present invention, the coating line process, multivariate conditions of the composite layer, and film structure can be adjusted to control the viscosity of the coating liquid and thin the multilayer film.

Figure 12 schematically shows the equipment and coating method used in the film coating process. In the present invention, the thickness of the film can be adjusted to 50㎛ or less, preferably 10㎛ or less, and the layer thickness can be adjusted to 20㎛ or less, preferably 5㎛ or less, through multilayer film process design using a 3 head coat line. there is.

In the present invention, gravure coating, slot die coating, Mayer bar coating, doctor blade, etc. may be used as the coating method. Figure 13 shows a coating apparatus used in an exemplary embodiment of the present invention. In the present invention, for example, a micro gravure coater (Yasui Seiki, Japan) can be used, and it is also possible to use a nano coater combining slot die and Mayer bar coating.

Specifically, in the present invention, a microgravure roll was selected in the coating process and the process was optimized using adhesive preparation and vacuum defoaming technology. Microgravure rolls can be manufactured by Japan's OSP, and process conditions such as reverse M/G ratio and doctor knife angle can be adjusted. Figure 14 shows the structure of a coating roll used in an exemplary embodiment of the present invention.

In a film with a multilayer structure, each layer may have different characteristics as shown in Figure 15, and accordingly, interfacial peeling may occur as shown in Figure 16. In the present invention, in order to solve problems such as deformation resistance, reduced product reliability, and reduced performance due to interlayer bonding when manufacturing a multi-layer film, the interfacial peeling bond force is measured to analyze the fracture shape at the microinterface, and the fracture shape is analyzed in various layer structures. The vulnerabilities were analyzed and applied to the expansion of the product line through the establishment of a database (DB). In addition, the relationship between interfacial bonding force and reliability was analyzed, and guidelines for product design direction were secured.

In the present invention, the multi-layer film coating process was optimized to manufacture layers with different characteristics into a single film to increase durability and user convenience, and to solve the problem of decreased transparency due to particle size and dispersion, nano/organic materials were used. A complex distributed system was introduced. In addition, using the present invention, the adhesion can be controlled according to the adherend surface and the user's environment, thereby minimizing surface damage, increasing operator convenience, and ensuring long-term durability.

In addition, according to the present invention, durability is enhanced by using PET/TPU film as a base film, and excellent flexibility can be secured by controlling the thickness of the film. In addition, the expression of antibacterial/antiviral properties can be maximized by controlling surface wettability.

Example

The present invention will be described in more detail through examples below. However, these examples show some experimental methods and compositions to illustratively illustrate the present invention, and the scope of the present invention is not limited to these examples.

Table 1 shows the antibacterial activity measurement results (bacteria count/cm ² , antibacterial activity log) of the coating film manufactured according to an example of the present invention, and Figure 17 shows a photo of the antibacterial activity test.

As a result of measuring the antibacterial activity using the film adhesion method of JIS Z 2801, it was confirmed that the coating according to the present invention exhibited antibacterial properties of 4.4 to 5.2, that is, 99.995 to 99.999%. Different characteristics are expressed depending on the structure or coating method of the coating film, and simply using a lot of inorganic particles does not produce excellent results, and the most effective performance is achieved when the antibacterial layer and the film layer are separated rather than when the film itself is coated. It can be.

Table 2 shows the results of measuring antibacterial activity for various particles and components. According to the present invention, it is possible to overcome the technical limitation that even if antibacterial or antiviral properties are expressed at the single particle stage, the same performance is not expressed when filmed.

Figure 18 shows a photograph of the surface of a coating film to which composite particles were applied according to an embodiment of the present invention, Figure 19 shows the durability measurement results of a material to which composite particles were applied, and Figure 20 shows the antibacterial/antibacterial properties of a surface to which composite particles were applied. This shows the results of measuring antiviral properties.

According to the above experimental results, it can be confirmed that the coating film of the present invention has excellent durability and high antibacterial activity.

As seen above, the antibacterial or antiviral coating composition according to the present invention has excellent dispersibility and adhesion, can control the performance of the coating by adjusting the properties of the ingredients, has excellent process convenience, and can be easily formed into a thin film. can be formed. In addition, when an antibacterial or antiviral film is manufactured using the coating composition of the present invention, interfacial peeling that occurs in a multilayer structure is prevented, transparency is excellent, antibacterial or antiviral properties are excellent, and a flexible film can be manufactured.

As the specific parts of the present invention have been described in detail above, those skilled in the art will understand that these specific descriptions are merely preferred embodiments and do not limit the scope of the present invention. will be clear. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (11)

An antibacterial or antiviral coating composition comprising inorganic nanoparticles and polymers.
According to claim 1,
An antibacterial or antiviral coating composition wherein the polymer is a copolymer prepared using an acrylate-based monomer.
According to claim 1,
An antibacterial or antiviral coating composition wherein the polymer contains one or more functional groups selected from the group consisting of an alkyl group, an aryl group, a carboxyl group, a hydroxy group, a thiol group, and an isocyanate group in the molecule.
According to claim 1,
An antibacterial or antiviral coating composition prepared using a binder precursor where the polymer includes a backbone compatible with the filler, a photocurable functional group, and a ring-opening thermosetting functional group.
According to claim 1,
An antibacterial or antiviral coating composition wherein the inorganic nanoparticles include at least one selected from the group consisting of single-structured metal nanoparticles, composite metal nanoparticles, and metal ceramic composite particles.
According to claim 1,
An antibacterial or antiviral coating composition wherein the inorganic nanoparticles include one or more metal components selected from the group consisting of copper, gold, silver and zinc.
According to claim 1,
An antibacterial or antiviral coating composition in which the inorganic nanoparticles are processed using an electron beam.
An antibacterial or antiviral film comprising a coating layer formed by coating the coating composition according to claim 1.
According to claim 8,
An antibacterial or antiviral film, wherein the coating is performed using gravure coating, slot die coating, Meyer bar coating or doctor blade.
According to claim 8,
An antibacterial or antiviral film, wherein the film is hydrophilic or water-repellent.
Applying the coating composition according to claim 1; Photocuring the applied composition; And a method for producing an antibacterial or antiviral film, comprising the step of heat curing.