KR102413388B1 - Polycarbonate anti-microbial film and manufacturing method for the same - Google Patents

Abstract

The disclosed content relates to a polycarbonate antibacterial film that is not only harmless to the human body by adding a silver-based antibacterial agent internally to the polycarbonate film, but also has antibacterial performance semi-permanently, and a method for manufacturing the same.
The polycarbonate antibacterial film is made of polycarbonate, and may include a polycarbonate film having fine concavities and convexities formed on the upper and lower surfaces, respectively, and a silver-based antibacterial agent internally attached to the polycarbonate film.

Description

Polycarbonate antibacterial film and its manufacturing method

The content disclosed in the present specification relates to a polycarbonate antibacterial film in which antibacterial performance is maintained semi-permanently and a method for manufacturing the same.

Unless otherwise indicated herein, the material described in this section is not prior art to the claims of this application, and inclusion in this section is not an admission that it is prior art.

Recently, as the bacterial infection situation has been prolonged due to Corona 19, the popularity and consumption of various antibacterial products such as smartphone antibacterial film, antibacterial deodorant, antibacterial cutting board, and antibacterial dishcloth are gradually increasing. In particular, in relation to infection, antibacterial films are being installed in places that people can reach, such as elevators and door handles, at government offices, companies, hospitals, hotels, marts, department stores, and apartments. In addition, in schools, kindergartens, daycare centers, and private institutes where children with weak immunity live, antibacterial films are installed on desks, handles and dining tables to suppress the growth of pathogens such as viruses and bacteria. Some are raising questions about the antibacterial performance of these antibacterial films, and manufacturers of the products are rushing to research and develop products to improve problems and produce better products.

As an example of a related technology, Patent Document 1 includes 0.05 wt% to 0.5 wt% of nano zinc oxide having a particle diameter of 1 nm to 50 nm in a synthetic resin raw material, and the synthetic resin raw material is polyethylene (PE), poly It is disclosed for a synthetic resin antibacterial film made of any one of propylene (PP), polyethylene terephthalate (PET), ethylene vinyl acetate (EVA), polyvinyl chloride (PVC), and polyamide (PA), and Patent Document 2 includes letters, The pattern shape and logo are gravure printed on the outer surface, and the inner film has an antibacterial treatment on the inner surface, the outer film laminated on the printing surface of the inner film, and the outer film of the packaging material film formed of the inner film and the outer film. Transparent silver nano is on the outer surface. Disclosed is a gravure-printed silver nano antibacterial packaging film configured by forming a coated outer silver nano coating.

Patent Document 1 is a synthetic resin raw material, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), ethylene vinyl acetate (EVA), polyvinyl chloride (PVC), polyamide (PA) in any one of nano Although zinc oxide was applied, the durability of the raw material is low, so there is a limit to maintaining the antibacterial performance. Patent Document 2 provides silver nano-coated on the outer surface of the outer film, but this is also provided at the outermost side, so that it is antibacterial by friction with the outside. There is a problem in that performance is easily lost.

Republic of Korea Patent Publication No. 10-2020-0045601 (2020.05.06) Republic of Korea Patent Registration No. 10-0800611 (2008.01.28)

An object of the present invention is to provide a polycarbonate antibacterial film in which antibacterial performance is semi-permanently sustained by internally adding a silver-based antibacterial agent to the polycarbonate film and a method for manufacturing the same.

In addition, it is not limited to the technical problems as described above, and it is obvious that another technical problem may be derived from the following description.

According to an embodiment of the present disclosure, the polycarbonate antibacterial film is made of polycarbonate, and includes a polycarbonate film having fine concavities and convexities formed on the upper and lower surfaces, respectively, and a silver-based antibacterial agent internally attached to the polycarbonate film.

In addition, the thickness of the polycarbonate film may be 50㎛ to 300㎛.

In addition, the fine irregularities may be formed by extrusion using a rubber roll made of silicon rubber and quartz powder.

In addition, the surface roughness (Ra) of the fine irregularities may be 0.5㎛ to 2.5㎛.

In addition, the silver-based antibacterial agent may be included in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of the polycarbonate.

In addition, the silver-based antibacterial agent may have an average particle diameter of 1.0 μm to 10 μm.

According to another embodiment of the present disclosure, the method for manufacturing a polycarbonate antibacterial film comprises the steps of (a) preparing an antibacterial masterbatch containing a silver-based antibacterial agent, (b) polycarbonate and the antibacterial masterbatch prepared in step (a) mixing and melting, (c) extruding the mixture melted in step (b) to form a film, and (d) forming fine concavities and convexities on the surface of the film extruded in step (c) And, the silver-based antibacterial agent is internally added to the film of step (c).

In addition, the antibacterial masterbatch in step (a) may be prepared by mixing 100 parts by weight of polycarbonate, 1 to 10 parts by weight of a silver-based antibacterial agent, 0.1 to 1 parts by weight of an antioxidant, and 0.01 to 0.5 parts by weight of a lubricant and then extruding. .

In addition, in step (b), 80 to 100 parts by weight of polycarbonate and 1 to 20 parts by weight of the antibacterial masterbatch may be mixed.

In addition, in step (d), the fine irregularities may be formed by extrusion using a rubber roll made of silicone rubber and quartz powder.

According to one embodiment disclosed in the present specification, the polycarbonate antibacterial film is harmless to the human body as the silver-based antibacterial agent is internally added to the polycarbonate film, and the antibacterial performance is semi-permanent.

In addition, by applying a silver-based antibacterial agent having a particle diameter of 1.0 μm to 10 μm, the contact area between pathogens is increased, and even containing a small amount of the silver-based antibacterial agent can exert antibacterial and sterilizing power on pathogens, so there is an economical effect.

According to another embodiment disclosed herein, the method for producing a polycarbonate antibacterial film comprises mixing and melting an antibacterial masterbatch prepared by mixing polycarbonate and a silver-based antibacterial agent with polycarbonate, and extruding the polycarbonate, whereby the silver-based antibacterial agent is uniform in the polycarbonate. It has a very good antibacterial effect.

1 is a perspective view showing a polycarbonate antibacterial film according to an embodiment of the content disclosed herein.
FIG. 2 is a cross-sectional view of FIG. 1 .
3 is a cross-sectional view showing another form of the fine irregularities.
Figure 4 is a process diagram for explaining a method of manufacturing a polycarbonate antibacterial film according to another embodiment of the disclosure disclosed herein.
5 and 6 are photographs showing the antibacterial performance evaluation results of Experimental Example 1.

Advantages and features of the present invention, and a method for achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the technical field to which the present invention belongs It is provided to fully inform the possessor of the scope of the invention, and the present invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout.

In describing the embodiments of the present invention, if it is determined that a detailed description of a well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the terms to be described later are terms defined in consideration of functions in an embodiment of the present invention, which may vary according to intentions or customs of users and operators. Therefore, the definition should be made based on the content throughout this specification.

1 is a perspective view showing a polycarbonate antibacterial film according to an embodiment of the content disclosed herein, FIG. 2 is a cross-sectional view taken along line A-A' of FIG. 1, and FIG. 3 is a cross-sectional view showing another form of fine irregularities.

Hereinafter, a polycarbonate antibacterial film according to an embodiment of the disclosure will be described with reference to FIGS. 1 to 3 .

1 to 3, the polycarbonate antibacterial film 100 disclosed herein is made of polycarbonate (PC), and the polycarbonate film ( 10) and a silver-based antibacterial agent 20 internally attached to the polycarbonate film 10 .

The polycarbonate film 10 is made of polycarbonate, and fine irregularities 30 and 40 may be formed on the surfaces of the upper and lower surfaces of the polycarbonate film 10 , respectively. In addition to the embossing pattern shown in FIG. 2 , the fine irregularities 30 and 40 may be applied to a wave pattern in which the curved convex and concave parts shown in FIG. 3 intersect. In addition, although not shown in the drawings, the shapes of the fine irregularities 30 and 40 formed on the upper and lower surfaces of the polycarbonate film 10 may be different from each other, of course. The fine irregularities 30 and 40 are not flat and have a curve, so that roughness can be imparted to the surface and glare and scratches can be prevented at the same time. In this case, the surface roughness (Ra) may be 0.5 μm to 2.5 μm, preferably 0.9 μm to 1.2 μm, and more preferably 1.0 μm.

On the other hand, the fine irregularities 30 and 40 may be formed by extrusion by means of a rubber roll on which the fine irregularities are formed. The rubber roll is formed by coating a high-temperature hardening silicone rubber with a thickness of 2 mm to 10 mm on the outer surface of a substrate made of steel. It may be formed by applying a mixture of 100 parts by weight of room temperature curable silicone rubber and 40 to 300 parts by weight of quartz powder to the outer surface of the high temperature curable silicone rubber to a thickness of 5 mm to 10 mm and then polishing. The rubber roll will be described in detail below.

The thickness t ₁ of the polycarbonate film 10 may be 50 μm to 300 μm, preferably 100 μm to 180 μm, and more preferably 150 μm. If the thickness (t ₁ ) of the polycarbonate film 10 is less than 50 μm, durability may be reduced, and if it exceeds 300 μm, durability may be secured, but it may be difficult to implement a desired elongation. When the polycarbonate film 10 satisfies the above-mentioned range, it is excellent in flame retardancy and can implement appropriate workability and durability.

The silver-based antibacterial agent 20 may be provided by being internally attached to a polycarbonate film, and may include a silver-based organic antibacterial agent, a silver-based inorganic antibacterial agent, and a silver-based ion exchanger. It may be in the form of fine particles of 10 μm, preferably 2.5 μm. The conductivity of silver is the highest among all metals except platinum, and this is the same as saying that it has the lowest electrical resistance. The silver-based antibacterial agent 20 increases the contact area between pathogens such as bacteria, fungi, and viruses, and has excellent antibacterial and sterilization effects to the extent that it is known that there is no bacteria that can survive for more than 6 minutes in contact with silver.

Meanwhile, the silver-based antimicrobial agent 20 may be included in an amount of 0.1 to 1 part by weight, preferably 0.2 to 0.6 part by weight, based on 100 parts by weight of the polycarbonate. If the amount of the silver-based antimicrobial agent 20 is less than 0.1 parts by weight, the antibacterial activity may be insignificant, and if it exceeds 1 part by weight, the synergistic effect may not be so great due to the content exceeding necessary.

For example, the silver-based antibacterial agent 20 is preferably an inorganic silver-based antibacterial agent, silver-based zirconium phosphate, silver-based zeolite, silver-based glass-based or at least one of a silver-based glass and zeolite compound, more preferably a silver-based glass-based compound may be used.

In addition, the silver-based antibacterial agent 20 may further include an antioxidant and a lubricant.

The antioxidant is a substance added to prevent deterioration of quality by preventing the resin from easily oxidizing by reacting with air. At least one of phenolic, amine, sulfur, phosphate and phosphorus can be selected and used. Among commercially available antioxidants, phenolic agents include Irganox 1076 (BASF), AO-60/AO-60G (ADEKA), and ETHANOX ^® 310 (ALBEMARLE), and phosphate-based antioxidants include Irgafos 168 (BASF), ETHAPHOS ^TM 368 ( ALBEMARLE) and Hostanox ^® P-EPQ ^® FF (Clariant).

The lubricant is a material used to facilitate processing by improving fluidity when heat-molding a resin, and includes metal stearate, ester, amide, and paraffin. At least one of them, preferably a metal stearate-based (metal stearate) may be used. Commercially available lubricants include, for example, Hi-Lube (Shinwon Chemical), Mg-St (Songwon), Ca-St (Songwon), Zn-St (Songwon), AX-71 (ADEKA), Loxiol ^® P-861 (Emery) and others.

Hereinafter, a method of manufacturing the polycarbonate antibacterial film disclosed in the present specification will be described in detail with reference to the drawings.

Figure 4 is a process diagram for explaining a method of manufacturing a polycarbonate antibacterial film according to another embodiment of the disclosure disclosed herein.

Referring to FIG. 4 , first, an antibacterial masterbatch containing a silver-based antibacterial agent is prepared (S10).

1 to 10 parts by weight of the silver-based antibacterial agent to 100 parts by weight of the polycarbonate, preferably 2 to 8 parts by weight, more preferably 4.5 parts by weight, 0.1 to 1 part by weight of the antioxidant, preferably 0.3 to 0.5 parts by weight, more preferably Preferably, 0.4 parts by weight and 0.01 to 0.5 parts by weight of a lubricant, preferably 0.1 to 0.3 parts by weight, more preferably 0.2 parts by weight, and then extruded by a twin extruder can be pelletized.

The silver-based antibacterial agent can be uniformly dispersed in the polycarbonate by mixing and melting the antibacterial masterbatch prepared as described above with polycarbonate to be described later and extrusion molding, so that the antibacterial activity can be excellent.

Then, the polycarbonate and the antibacterial masterbatch are mixed and melted (S20).

80 to 100 parts by weight of polycarbonate, preferably 85 to 95 parts by weight, more preferably 90 parts by weight and 1 to 20 parts by weight of the antibacterial masterbatch prepared in step S10, preferably 5 to 15 parts by weight, more Preferably, 10 parts by weight may be put into an extruder provided in a hopper dryer, and melted by mixing and heating. The heating may be carried out at a temperature of 250 °C to 290 °C, preferably 260 to 280 °C.

If the polycarbonate is less than 80 parts by weight, the durability may be poor, and if it exceeds 100 parts by weight, the flame retardancy and workability may be poor.

If the antibacterial masterbatch is less than 1 part by weight, the antibacterial activity may be insignificant, and if it exceeds 20 parts by weight, the synergistic effect according to the content more than necessary may not be so great. Therefore, it is most preferable to mix in the above-mentioned content range.

Thereafter, the molten mixture is extruded to form a film (S30).

The mixture molten in step S20 may be extruded in the form of a film through a nozzle provided in the extruder and a die connected to the nozzle, and the extruder is not particularly limited in its use as long as it is typically used to produce a polycarbonate film.

The extruded film may be in a state in which a silver-based antibacterial agent is internally added. Specifically, although it is distributed in the film, it is also partially exposed on the surface, so it is easy to contact between pathogens, so that the pathogen can exert antibacterial and sterilizing power.

Finally, fine irregularities are formed on the surface of the extruded film (S40).

In the step S30, fine irregularities may be formed on the surface of the extruded film, and in this case, the fine irregularities may be formed by extrusion using a rubber roll made of silicon rubber and quartz powder. The extrusion pressure may be in the range of 5 to 20 bar.

On the other hand, the rubber roll is made of 100 parts by weight of room temperature curing silicone rubber and 40 parts by weight to 300 parts by weight of quartz powder on the outer surface of the high temperature curing silicone rubber after high temperature curing silicone rubber is applied to the outer surface of a steel substrate to a thickness of 2 mm to 10 mm It can be formed by a process of grinding after applying the mixture to a thickness of 5 to 10 mm.

The quartz powder may have a particle size of 100 to 1000 mesh. This means that when the particle size of the quartz powder is less than 100 mesh, the quartz powder does not mix well with the liquid rubber and easily scatters to contaminate the workplace, and the effect of forming fine irregularities on the surface of the film is insignificant, exceeding 1000 mesh This is not preferable because, because the particle size of the quartz powder is too large, the surface roughness of the film is excessively increased, so that fine irregularities cannot be formed. Can not do it.

If the coating thickness of the high temperature curable silicone rubber is less than 2 mm, the adhesion to the substrate is insignificant.

Example 1. Preparation of antibacterial masterbatch

After mixing 4.5 parts by weight of silver-based glass having a particle size of 2.5 μm to 100 parts by weight of polycarbonate, 0.4 parts by weight of antioxidant and 0.2 parts by weight of lubricant, extruded with a twin extruder (Φ32, L/D=40) and pelletized to antibacterial A masterbatch was prepared.

Raw material name Content (parts by weight) polycarbonate 100 silver antibacterial agent silver glass 4.5 antioxidant metal stearate 0.4 skid N,N'-ethylene bis stearamide 0.2

Example 2. Preparation of polycarbonate antibacterial film

90% by weight of polycarbonate and 10% by weight of the antibacterial masterbatch prepared in Example 1 were put into an extruder equipped with a hopper dryer, and the temperature of the extruder cylinder was heated to 260°C to 280°C to melt the polycarbonate and the antibacterial masterbatch After that, the molten mixture was extruded in the form of a film through a nozzle provided in the extruder and a die connected to the nozzle. Then, a pressure of 20 bar was applied and extruded using a rubber roll having fine concavities and convexities formed on the surface of the film to prepare a 150 μm thick polycarbonate antibacterial film having fine concavities and convexities.

Experimental Example 1. Evaluation of antibacterial performance

In order to evaluate the antimicrobial activity of the polycarbonate antibacterial film of Example 2, an experiment was conducted according to the JIS Z 2801 (film adhesion method) test method.

Staphylococcus aureus ATCC 6538P (strain 1) and Escherichia coli ATCC 8739 (strain 2) were used as test strains, and Stomacher ^® POLY-BAG was used as a control.

First, a test bacterial solution was prepared for each strain, and the initial number of bacteria was measured and described in Table 2 below. The polycarbonate antibacterial film of Example 1 and Stomacher ^® POLY-BAG of the control were prepared in a size of 5 cm × 5 cm, respectively, and 0.4 ml of the test bacterial solution was dripped onto the film, and then the cover film was covered. And the number of bacteria was measured after stationary culture for 24 hours under the conditions of 35±1° C. and 90% RH, and the results are shown in Table 2 and FIGS. 5 and 6 below. In Table 2, the unit of the number of bacteria is the number of bacteria/cm ² , and the unit of the antibacterial activity value is log. % calculation of the antibacterial activity value can be applied to Equation 1 below.

division Example 1 control Staphylococcus aureus initial number of bacteria - 1.8×10 ⁴ after 24 hours <0.63 3.0×10 ⁴ Antibacterial activity (%) 4.6 (99.9%) - coli initial number of bacteria - 1.5×10 ⁴ after 24 hours 7.9×10 9.8×10 ⁵ Antibacterial activity (%) 4.0 (99.9%) -

Referring to Table 2 and FIGS. 5 and 6, in the control group, there is almost no antibacterial activity in both Staphylococcus aureus and E. coli, whereas in Example 1, the antibacterial activity value in Staphylococcus aureus and Escherichia coli was 99.9%, respectively. could check

Although preferred embodiments of the present invention have been described with reference to the accompanying drawings, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention and represent all of the technical spirit of the present invention. Therefore, it should be understood that there may be various equivalents and modifications that can be substituted for them at the time of filing the present application. Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all respects, and the scope of the present invention is indicated by the following claims rather than the detailed description, and the meaning and scope of the claims and their All changes or modifications derived from the concept of equivalents should be construed as being included in the scope of the present invention.

100: polycarbonate antibacterial film 10: polycarbonate film
20: silver antibacterial agent 30, 40: fine irregularities

Claims (10)

A polycarbonate film made of polycarbonate, each of which is formed with fine concavities and convexities on the upper and lower surfaces; and
A silver-based antibacterial agent internally added to the polycarbonate film, wherein the silver-based antibacterial agent is silver-based glass, the average particle diameter is 1.0 μm to 10 μm, and further includes an antioxidant and a lubricant,
The fine concavities and convexities are formed by extrusion with a rubber roll made of silicon rubber and quartz powder, and the particle size of the quartz powder is 100 to 1000 mesh, and the surface roughness (Ra) of the fine concavities and convexities is 0.5 μm to 2.5 μm. polycarbonate antibacterial film.
According to claim 1,
Polycarbonate antibacterial film, characterized in that the thickness of the polycarbonate film is 50㎛ to 300㎛.
delete delete According to claim 1,
The silver-based antibacterial agent is polycarbonate antibacterial film, characterized in that it is contained in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the polycarbonate.
delete (a) preparing an antimicrobial masterbatch comprising a silver-based antimicrobial agent;
(b) mixing and melting 80-100 parts by weight of polycarbonate and 1-20 parts by weight of the antibacterial masterbatch prepared in step (a);
(c) extruding the molten mixture in step (b) to form a film; and
(d) forming fine irregularities on the surface of the film extruded in step (c);
In step (a), the antibacterial masterbatch is prepared by mixing 100 parts by weight of polycarbonate, 1 to 10 parts by weight of a silver-based antibacterial agent, 0.1 to 1 parts by weight of an antioxidant, and 0.01 to 0.5 parts by weight of a lubricant, followed by extrusion, and the silver-based antibacterial agent is It is silver-based glass, and the average particle diameter is 1.0 μm to 10 μm,
The silver-based antibacterial agent is internally added to the film of step (c),
In step (d), the fine irregularities are formed by extrusion with a rubber roll made of silicon rubber and quartz powder, and the particle size of the quartz powder is 100 to 1000 mesh, and the surface roughness (Ra) of the fine irregularities is 0.5 μm to Method for producing a polycarbonate antibacterial film, characterized in that 2.5㎛. delete delete delete

Images