KR20220057236A - Anti-microbial sheet and manufacturing method for the same - Google Patents

Abstract

Disclosed are a co-extruded multilayer antimicrobial sheet which has antimicrobial performance that lasts semi-permanently and a manufacturing method thereof. The antimicrobial sheet comprises: a base layer; and first and second antimicrobial layers which are formed on upper and lower surfaces of the base layer, respectively, and have a silver-based antimicrobial agent added internally. The base layer and the first and second antimicrobial layers can be formed in a co-extrusion method by using an extruder.

Description

Antibacterial sheet and its manufacturing method {ANTI-MICROBIAL SHEET AND MANUFACTURING METHOD FOR THE SAME}

The content disclosed in the present specification relates to a co-extrusion multilayer antibacterial sheet 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, antibacterial films are installed on desks, handles and dining tables in schools, kindergartens, daycare centers, and private institutes where children with weak immunity live 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 discloses a method for manufacturing a silver nano-coated surface material in which a PP fabric and a PET fabric are laminated, and a silver nano-coating resin is applied to the PET fabric and coated. , pattern shape and logo are gravure printed on the outer surface, 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 on the outer surface Disclosed is a gravure-printed silver nano antibacterial packaging film configured by forming a silver nano-coated outer coating part.

The above Patent Documents 1 and 2 are manufactured by laminating films, so physical properties such as physical properties are inferior, and by providing silver nanoparticles as a coating type on the outer surface of the outer film, the antibacterial performance is easily lost due to friction with the outside. There is this.

Republic of Korea Patent No. 10-0753752 (2007.08.23) Republic of Korea Patent Registration No. 10-0800611 (2008.01.28)

An object of the present invention is to provide an antibacterial sheet having a multilayer structure in which the antibacterial performance is semi-permanently maintained while minimizing the decrease in physical properties by applying the co-extrusion method, 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 disclosure, the antibacterial sheet is formed on the base layer, the upper and lower surfaces of the base layer, respectively, and includes first and second antibacterial layers to which a silver-based antibacterial agent is internally added, the base layer and the first and the second antibacterial layer is formed by a co-extrusion method using an extruder.

In addition, the base layer is polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (polyimide, PI), polyethersulfone (polyethersulfone, PES), polyarylate (polyarylate, PAR) ), polyethylene naphthalate (PEN), and polyethylene terephthalate (PET) may be at least one selected from the group consisting of.

In addition, the thickness of the base layer may be 1 ~ 15mm.

In addition, the first and second antibacterial layers are polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), polyethersulfone (PES), polyarray At least one resin selected from polyarylate (PAR), polyethylene naphthalate (PEN), and polyethylene terephthalate (PET) contains 80 to 99% by weight and 1 to 20% by weight of an antibacterial masterbatch However, the antibacterial masterbatch may include 100 parts by weight of polycarbonate (PC), 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.

In addition, the thickness of the first and second antibacterial layers may be 10 ~ 200㎛, respectively.

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

In addition, the extruder is an extrusion die for making a sheet shape, coupled to the extrusion die, a first supply unit for supplying the raw material of the base layer, coupled to the extrusion die, the agent for supplying the raw material of the first and second antibacterial layer 2 It may include a cooling unit for cooling the antibacterial sheet extruded from the supply unit and the extrusion die.

In addition, the first supply unit may include a first hopper and a first transfer screw provided between the first hopper and the extrusion die to transfer the raw material of the base layer from the first hopper to the extrusion die.

In addition, the second supply unit is provided between the second hopper and the second hopper and the extrusion die, and the second and third transfers for transferring the raw materials of the first and second antibacterial layers from the second hopper to the extrusion die, respectively. It may include a screw.

In addition, the extrusion die includes a first flow path, second and third flow paths respectively formed on the upper and lower portions of the first flow path, the first flow path is supplied with the raw material of the base layer, the second and second Raw materials for the first and second antibacterial layers may be respectively supplied to the third flow path.

According to one embodiment disclosed in the present specification, the antibacterial sheet is harmless to the human body as well as the antibacterial performance is semi-permanent because the silver-based antibacterial agent is formed on the upper and lower surfaces of the base layer by the co-extrusion method.

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.

1 is a perspective view showing an antibacterial sheet according to an embodiment of the content disclosed in the present specification.
FIG. 2 is a cross-sectional view taken along line A-A' of FIG. 1 .
3 is a side view showing the extruder.
4 is a schematic view showing the extrusion die in FIG.
5 and 6 are photographs showing the antibacterial performance evaluation results of Experimental Example 2.

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 an antibacterial sheet according to an embodiment of the disclosure disclosed herein, and FIG. 2 is a cross-sectional view taken along line A-A' of FIG. 1 .

Hereinafter, an antibacterial sheet according to an embodiment of the disclosed subject matter will be described with reference to FIGS. 1 and 2 .

The antibacterial sheet 100 disclosed herein is formed on the base layer 110, the upper and lower surfaces of the base layer 110, respectively, and the first and second antibacterial layers 120 and 130 to which the silver-based antibacterial agent 140 is internally added. ) is included. In addition, the base layer 110 and the first and second antibacterial layers 120 and 130 may be formed by a co-extrusion method using the extruder 1 , specifically, a calender roll method. The thickness of such an antibacterial sheet 100 may be in the range of 2 to 15 mm, preferably 5 to 12 mm.

In the past, it was manufactured by putting an antibacterial agent in an antibacterial sheet with a thickness of 1 to 15 mm. In this case, there was a problem in that the amount of the antimicrobial agent was increased, so that the unit price was increased, the light transmittance was decreased, and the haze was increased. Accordingly, in this embodiment, when the coextrusion method using the extruder 1 is applied and applied to the upper and lower surfaces of the base layer, the antibacterial, transmittance and haze performance can be secured, and the cost can be reduced by adding a small amount of antibacterial agent to a thin thickness. Do.

The base layer 110 is polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (polyimide, PI), polyethersulfone (polyethersulfone, PES), polyarylate (polyarylate, PAR), polyethylene naphthalate (PEN), and at least one selected from polyethylene terephthalate (PET), preferably polycarbonate (PC), but may be made of rigidity and transparency If there is a substance, its use is not significantly restricted.

On the other hand, the thickness (t ₁ ) of the base layer 110 may be 1 ~ 15mm, preferably 1.8 ~ 14.8mm. If the thickness (t ₁ ) of the base layer 110 is less than 1 mm, durability may be reduced, and if it exceeds 15 mm, durability may be secured, but it may be difficult to implement a desired elongation. When the base layer 110 satisfies the above-mentioned range, appropriate processability and durability may be realized.

The first and second antibacterial layers 120 and 130 are layers having antibacterial performance, and include polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), and poly 80 to 99% by weight of at least one resin selected from ethersulfone (PES), polyarylate (PAR), polyethylene naphthalate (PEN), and polyethylene terephthalate (PET), and It may contain 1 to 20% by weight of the antibacterial masterbatch.

If the resin is less than 80% by weight, the durability may be poor, and if it exceeds 99% by weight, the flame retardancy and workability may be poor.

If the antibacterial masterbatch is less than 1% by weight, the antibacterial activity may be insignificant, and if it exceeds 20% 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.

The antibacterial masterbatch may include 100 parts by weight of polycarbonate (PC), 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.

If the amount of the silver-based antibacterial agent 140 is less than 1 part by weight, the antibacterial activity may be insignificant, and if it exceeds 10 parts by weight, the synergistic effect according to the content more than necessary may not be very large.

For example, the silver-based antibacterial agent 140 may be at least one selected from a silver-based organic antibacterial agent, a silver-based inorganic antibacterial agent, and a silver-based ion exchanger, preferably an inorganic silver-based antibacterial agent. As the inorganic silver-based antibacterial agent, silver-based zirconium phosphate, silver-based zeolite, silver-based glass-based or at least one selected from silver-based glass and zeolite compounds may be used, but silver-based glass-based compounds are preferably used.

In the case of the existing nano-sized silver-based antibacterial agent, it can easily enter the human body and be harmful to the human body due to its small size. Therefore, in this embodiment, the average particle size of the silver-based antibacterial agent 140 is adjusted to 1.0 μm to 10 μm, preferably 2.5 μm, thereby preventing the inflow into the human body and is harmless to the human body. Silver has the highest conductivity among all metals except platinum, and this is the same as saying that it has the lowest electrical resistance. The silver-based antibacterial agent 140 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 thickness t ₂ of the first antibacterial layer 120 and the thickness t ₃ of the second antibacterial layer 130 may be 10 μm to 200 μm, respectively. If the thickness (t ₂ , t ₃ ) of the first and second antibacterial layers 120 and 130 is less than 10 μm, antibacterial performance and durability may be reduced, and if it exceeds 200 μm, antibacterial performance and durability are secured However, the overall thickness becomes thicker, and it may be difficult to achieve the desired elongation. When the first and second antibacterial layers 120 and 130 satisfy the above-mentioned ranges, appropriate processability and durability may be implemented.

The antioxidant is a substance added to prevent deterioration of quality by preventing the resin from being easily oxidized 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), Hostanox ^® P-EPQ ^® FF (Clariant), and the like.

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.

The first and second antibacterial layers 120 and 130 disclosed in this embodiment are not prepared using a silver-based antibacterial agent and resin, but are manufactured using an antibacterial masterbatch and a resin containing a silver-based antibacterial agent. Since it can be more uniformly dispersed in the resin, antibacterial performance can be improved.

Hereinafter, the extruder disclosed herein will be described in detail with reference to the drawings.

Figure 3 is a side view showing the extruder, Figure 4 is a schematic view showing the extrusion die in Figure 3.

Referring to FIG. 3 , the extruder 1 includes an extrusion die 10 making a sheet shape, a first supply unit 20 coupled to the extrusion die 10 , and supplying a raw material of the base layer 110 , the extrusion It is coupled to the die 10, and the second supply unit 30 for supplying raw materials of the first and second antibacterial layers 120 and 130 and cooling for cooling the antibacterial sheet 50 extruded from the extrusion die 10 A portion 40 may be included.

As shown in FIG. 4, the extrusion die 10 includes a first flow path 11, and second and third flow paths 12 and 13 that are spaced apart from each other on the upper and lower portions of the first flow path 11, and , The first flow path 11 is supplied with the raw material of the base layer 110, and the second and third flow paths 12 and 13 are supplied with the raw material of the first and second antibacterial layers 120 and 130, respectively. can be

The first supply unit 20 is provided between the first hopper 21 and the first hopper 21 and the extrusion die 10, from the first hopper 21 to the extrusion die 10, the substrate layer ( 110) may include a first transfer screw 25 for transferring the raw material. For example, the first feed screw 25 may be connected to the first flow path 11 of the extrusion die 10 to melt and supply the raw material of the base layer 110 . In addition, the first transfer screw 25 may adjust the melting temperature by controlling the speed, the melting temperature may be in the range of 200 ~ 300 ℃.

The second supply unit 30 is provided between the second hopper 31 and the second hopper 31 and the extrusion die 10, and from the second hopper 31 to the extrusion die 10, the first and It may include second and third transfer screws 33 and 35 for transferring the raw materials of the second antibacterial layer 120 and 130 , respectively. For example, the second conveying screw 33 is connected to the second flow path 12 of the extrusion die 10 , and the third conveying screw 35 is connected to the third flow path 13 of the extrusion die 10 . As a result, the raw materials of the first and second antibacterial layers 120 and 130 may be melted and supplied, respectively. The second and third feed screws 33 and 35 can also adjust the melting temperature by adjusting the speed, and the speeds of the second and third feed screws 33 and 35 are the same, but the speed of the first feed screw 25 is the same. It may be slower than the speed. Since the non-uniformity of the melting temperature may cause a zigzag pattern and a wave pattern on the surface of the extruded antibacterial sheet 50, it is preferable to maintain a constant temperature by controlling the speed.

The cooling unit 40 may consist of a water tank in which cooling water is stored, and may cool the co-extrusion-formed antibacterial sheet 50 by passing through the extrusion die 10 .

Looking at the operation of the extruder 1 configured as described above, the raw material of the substrate layer 110 injected into the first hopper 21 of the first supply unit 20 is the extrusion die 10 by the first transfer screw 25 . The raw materials for the second and third antibacterial layers 120 and 130 that are transferred to the first flow path 11 and put into the second hopper 31 of the second supply unit 30 are second and third transfer screws 33, 35) to the second and third flow paths 12 and 13, respectively. Each of the transferred raw materials is passed through the extrusion die 10 to be co-extruded into the antibacterial sheet 50, and cooled by the cooling unit 40, the final antibacterial sheet can be obtained.

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 antibacterial sheet

Using an extruder, 100% by weight of polycarbonate is applied as a raw material for the base layer by applying a co-extrusion molding method, and 90% by weight of polycarbonate as a raw material for the second and third antibacterial layers and the antibacterial master prepared in Example 1 An antibacterial sheet was prepared by applying 10% by weight of the batch.

Experimental Example 1. Evaluation of antibacterial performance

In order to evaluate the antimicrobial activity of the antibacterial sheet 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 antibacterial sheet of Example 2 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 antibacterial sheet, and then a 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 the following equation (1).

division control Example 1 Staphylococcus aureus initial number of bacteria 1.8×10 ⁴ - after 24 hours 3.0×10 ⁴ <0.63 Antibacterial activity (%) - 4.6 (99.9%) coli initial number of bacteria 1.5×10 ⁴ - after 24 hours 9.8×10 ⁵ 1.0×10 Antibacterial activity (%) - 4.9 (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 Escherichia coli, whereas in Example 2, 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: antibacterial sheet 110: base layer
120: first antibacterial layer 130: second antibacterial layer
140: silver-based antibacterial agent 1: extruder
10: extrusion die 11: first flow path
12: 2nd Euro 13: 3rd Euro
20: first supply 21: first hopper
25: first feed screw 30: second supply unit
31: second hopper 33: second feed screw
35: third transfer screw 40: cooling unit
50: antibacterial sheet

Claims (10)

base layer;
It is formed on the upper and lower surfaces of the base layer, respectively, and includes first and second antibacterial layers to which a silver-based antibacterial agent is internally added,
The base layer and the first and second antibacterial layers are antibacterial sheet, characterized in that formed by a co-extrusion method by an extruder.
According to claim 1,
The base layer is an antibacterial sheet, characterized in that at least one selected from polycarbonate, polymethyl methacrylate, polyimide, polyether sulfone, polyarylate, polyethylene naphthalate, and polyethylene terephthalate.
According to claim 1,
The antibacterial sheet, characterized in that the thickness of the base layer is 1 ~ 15mm.
According to claim 1,
The first and second antibacterial layers,
80 to 99% by weight of at least one resin selected from polycarbonate, polymethyl methacrylate, polyimide, polyethersulfone, polyarylate, polyethylene naphthalate, and polyethylene terephthalate; and
1 to 20% by weight of the antibacterial masterbatch; including,
The antibacterial masterbatch,
100 parts by weight of polycarbonate;
1-10 parts by weight of silver-based antibacterial agent;
0.1 to 1 part by weight of antioxidant; and
Antibacterial sheet, characterized in that it contains; 0.01 to 0.5 parts by weight of lubricant.
According to claim 1,
The thickness of the first and second antibacterial layer is an antibacterial sheet, characterized in that each of 10 ~ 200㎛.
According to claim 1,
The silver-based antibacterial agent has an average particle diameter of 1.0㎛ to 10㎛ polycarbonate antibacterial sheet.
According to claim 1,
The extruder is
Extrusion die to make sheet shape;
a first supply unit coupled to the extrusion die and supplying a raw material for the base layer;
a second supply unit coupled to the extrusion die and supplying raw materials for the first and second antibacterial layers; and
Antibacterial sheet comprising a; a cooling unit for cooling the antibacterial sheet extruded from the extrusion die.
8. The method of claim 7,
The first supply unit,
first hopper; and
Antibacterial sheet, characterized in that it is provided between the first hopper and the extrusion die comprising a first transfer screw for transferring the raw material of the substrate layer from the first hopper to the extrusion die.
8. The method of claim 7,
The second supply unit,
second hopper; and
Antibacterial sheet, characterized in that it is provided between the second hopper and the extrusion die comprising a second and third transfer screws for transferring the raw materials of the first and second antibacterial layer from the second hopper to the extrusion die, respectively.
8. The method of claim 7,
The extrusion die,
1 Euro,
and second and third flow paths respectively formed on upper and lower portions of the first flow passage,
Antibacterial sheet, characterized in that the raw material of the base layer is supplied to the first passage, and the raw material of the first and second antibacterial layer is supplied to the second and third passages, respectively.

Images