KR102642479B1 - Manufacturing method of antibacterial and antiviral film - Google Patents

Abstract

The present invention relates to a method for manufacturing an antibacterial and antiviral film, and more specifically, a raw material mixing step of mixing a water-soluble silicic acid mixture with synthetic resin pellets, a drying step of drying the mixture prepared through the raw material mixing step, and the drying step. It consists of a molding step in which the dried mixture is extruded and formed into a film, and a cooling and winding step in which the molded product manufactured through the molding step is cooled and wound.
The film manufactured through the above process not only exhibits excellent antibacterial and antiviral properties because it contains a water-soluble silicic acid mixture, but also has an excellent far-infrared radiation effect, suppressing the growth of bacteria and mold, thereby suppressing the deterioration of the contents. .

Description

Method for manufacturing antibacterial and antiviral film {MANUFACTURING METHOD OF ANTIBACTERIAL AND ANTIVIRAL FILM}

The present invention relates to a method of manufacturing an antibacterial and antiviral film. More specifically, it not only exhibits excellent antibacterial and antiviral properties by containing a water-soluble silicic acid mixture, but also has an excellent far-infrared radiation effect, preventing the growth of microorganisms such as bacteria and mold. This relates to a method for manufacturing an antibacterial and antiviral film that has the effect of suppressing deterioration of the contents.

Previously, attempts were made to impart antibacterial properties to plastic products in various ways, mainly using organic antibacterial agents, inorganic antibacterial agents such as silver ions and zinc ions, and natural ingredients such as biological extracts or chitosan. Natural antibacterial agents were applied.

Organic antibacterial agents have strong antibacterial properties, but because they generally have a fast dissolution rate, the sustainability of the effect is low. They are made of ingredients harmful to the human body, so they are not suitable for the recent trend of emphasizing consumer safety, and they are made of synthetic resins. There was a problem of deteriorating the quality of the product by causing white turbidity in the raw materials or reducing gloss, etc.

In addition, inorganic antibacterial agents using silver ions or zinc ions are relatively safe and exhibit antibacterial properties against a wide range of bacteria, so they are used in various types of synthetic resin products. However, synthetic resins containing inorganic antibacterial agents composed of the above components have lower transparency. , discoloration and deterioration occurred relatively frequently, and manufacturing costs increased excessively.

In order to solve the above problems, methods for imparting antibacterial properties have been proposed, such as dispersing a fine powder antibacterial agent in a solvent such as alcohol, spraying or applying it to the surface of a molded product, or forming a surface coating layer containing an antibacterial agent. However, synthetic resin molded products are not treated with an antibacterial agent. When surface coating was done, there was a problem that scratches appeared on the surface of the molded product or the antibacterial performance deteriorated rapidly over time.

Accordingly, in order to solve the above problem, the present inventors found that mixing a water-soluble silicic acid mixture with a synthetic resin pellet not only has excellent antibacterial activity, but also emits far-infrared rays to exhibit excellent antibacterial and antiviral properties, thereby preventing deterioration of the contents. The present invention was completed by confirming that an antibacterial film could be provided.

Korean Patent Registration No. 10-0654185 (2006.11.29.) Korean Patent Registration No. 10-1007180 (2011.01.10.)

The purpose of the present invention is to provide an antibacterial and antiviral product that not only exhibits excellent antibacterial and antiviral properties by containing a water-soluble silicic acid mixture, but also has an excellent far-infrared radiation effect, suppressing the growth of bacteria and mold, thereby suppressing the deterioration of the contents. The purpose is to provide a method for manufacturing a film.

The purpose of the present invention is to include a raw material mixing step of mixing a water-soluble silicic acid mixture into synthetic resin pellets, a drying step of drying the mixture prepared through the raw material mixing step, and a molding step of extruding the dried mixture through the drying step and forming it into a film. This is achieved by providing a method for manufacturing an antibacterial and antiviral film, characterized in that it consists of a cooling and winding step of cooling and winding the molded product manufactured through the molding step.

According to a preferred feature of the present invention, the raw material mixing step is performed by mixing 0.1 to 1 part by weight of a water-soluble silicic acid mixture with 100 parts by weight of synthetic resin pellets.

According to a more preferred feature of the present invention, the synthetic resin pellet is made of one selected from the group consisting of polyethylene, polypropylene, polyurethane, and acrylonitrile butadiene styrene copolymer.

According to a more preferred feature of the present invention, the water-soluble silicic acid mixture contains at least one selected from the group consisting of SiO ₃ , Na ₂ SiO ₃ and Na ₂ SiO ₃ ·10H ₂ O.

According to an even more preferred feature of the present invention, the water-soluble silicic acid mixture includes a heating and melting step of heating and melting the silicate mineral, a maturing step of maturing the silicate mineral melted through the heating and melting step to obtain silicate crystals, and the maturing process. It is manufactured through a mixing and heating step in which purified water is mixed with the silicate crystals obtained through the step and heated.

According to an even more preferred feature of the present invention, the heating and melting step is performed by heating the silicate mineral at a temperature of 1500 to 2000° C. for 10 to 20 hours.

According to an even more preferred feature of the present invention, the ripening step is carried out for 10 to 20 days.

According to an even more preferred feature of the present invention, the mixing and heating step is performed by mixing 5000 to 15000 parts by weight of purified water with 100 parts by weight of the silicate crystals obtained through the aging step and heating to a temperature of 500 to 1000°C.

The method of manufacturing an antibacterial and antiviral film according to the present invention not only exhibits excellent antibacterial and antiviral properties by containing a water-soluble silicic acid mixture, but also has excellent far-infrared ray radiation effect to suppress the growth of bacteria and mold, thereby preventing deterioration of the contents. It has an excellent effect of providing an antibacterial and antiviral film that has an inhibitory effect.

Figure 1 is a flowchart showing a method for manufacturing an antibacterial and antiviral film according to the present invention.
Figure 2 is a flowchart showing the manufacturing process of the water-soluble silicic acid mixture used in the present invention.
Figures 3 and 4 are photographs taken by FE-SEM of the water-soluble silicic acid mixture prepared through Preparation Example 1 of the present invention.
Figure 5 is a photograph observing the antibacterial effect of the film prepared in Example 1 and Comparative Example 1 of the present invention.
Figure 6 is a photograph showing the results of measuring the far-infrared radiation effect of the film prepared in Example 1 of the present invention.

Below, preferred embodiments of the present invention and the physical properties of each component are described in detail, but are intended to be described in detail so that those skilled in the art can easily practice the invention. This does not mean that the technical idea and scope of the present invention are limited.

The method for producing an antibacterial and antiviral film according to the present invention includes a raw material mixing step (S101) of mixing a water-soluble silicic acid mixture with synthetic resin pellets, and a drying step (S103) of drying the mixture prepared through the raw material mixing step (S101). , a molding step (S105) of extruding the dried mixture through the drying step (S103) and forming it into a film, and a cooling and winding step (S107) of cooling and winding the molded product manufactured through the molding step (S105). .

The raw material mixing step (S101) is a step of mixing a water-soluble silicic acid mixture with synthetic resin pellets, and is achieved by mixing 0.1 to 1 part by weight of a water-soluble silicic acid mixture with 100 parts by weight of synthetic resin pellets and stirring at a speed of 100 rpm for 3 hours. Synthetic resin pellets are not particularly limited and any synthetic resin that can be molded into a film can be used. However, considering the physical properties of the film, it is selected from the group consisting of polyethylene, polypropylene, polyurethane, and acrylonitrile butadiene styrene copolymer. It is desirable to have it done as one.

The water-soluble silicic acid mixture serves to provide not only antibacterial and antiviral properties but also far-infrared radiation effects to the film produced through the present invention, and is a group consisting of SiO ₃ , Na ₂ SiO ₃ and Na ₂ SiO ₃ ·10H ₂ O It consists of one or more selected from.

In addition, the water-soluble silicic acid mixture includes a heating and melting step (S201) of heating and melting the silicate mineral, a maturing step (S203) of maturing the silicate mineral melted through the heating and melting step (S201) to obtain a silicate crystal, and the above It is manufactured through a mixing heating step (S205) in which purified water is mixed with the silicate crystals obtained through the maturation step (S203) and heated.

Silicate mineral, which is the raw material of the water-soluble silicic acid mixture, is a mineral composed of silicates and its main components are silicon and oxygen. Here, silicon (Si, Silicon) is the most important essential mineral among the 50 types of minerals essential to the human body. In the natural state, only silicon is independently present. It does not exist, but exists in the form of silicon dioxide (SiO ₂ ). If the purity of silicon is 100%, it becomes quartz. If it does not, it becomes quartz. If it contains a lot of other minerals, it becomes silica (marble). Because it is insoluble in water, it is unsuitable for human consumption, so it is generally used for industrial purposes. These silicate minerals can be classified into nesosilicate minerals, sorosilicate minerals, cyclosilicate minerals, inosilicate minerals, phyllosilicate minerals, and tectosilicate minerals depending on their bonding and arrangement states. In the present invention, silicate minerals include olivine, garnet, and zircon. , orthosite, gellenite, angiospermite, beryl, tourmaline, monoclinic pyroxene, rhombic hornblende, serpentine, kaolinite, orthosite, and plagioclase can be used.

The silicate mineral can be prepared by washing foreign substances on the surface several times with running water so as not to affect the heating and melting step (S201) or the maturation step (S203), which will be described later. In addition, it is prepared by grinding with any equipment selected from a ball mill, attrition mill, jet mill, rotary mill, and vibration mill. It's okay too.

The heating and melting step (S201) is performed by heating the silicate mineral at a temperature of 1500 to 2000°C for 10 to 20 hours. More specifically, the silicate mineral is heated in a furnace at a temperature of 1500 to 2000°C, preferably 1600 to 1700°C. This is the step of melting into a liquid state by heating at a temperature of 10 to 20 hours, preferably 12 to 15 hours.

At this time, if the heating temperature is less than 1500°C, it may be difficult for the silicate mineral to melt into a liquid state with fluidity and viscosity, and if the heating temperature exceeds 2000°C, the synergistic effect due to excess temperature supply is not very significant, This is undesirable because it only increases energy consumption.

In addition, if the heating time is less than 10 hours, it may be difficult to sufficiently melt the silicate mineral, and if the heating time exceeds 20 hours, the synergistic effect due to the heat treatment time longer than necessary is not so great, so it is necessary to maintain the heating time described above. It is desirable.

The aging step (S203) is performed for 10 to 20 days, and the silicate mineral melted through the heating and melting step (S201) is aged for 10 to 20 days, preferably 12 to 15 days to obtain silicate crystals. all.

At this time, if the maturation time is less than 10 days, it is difficult to obtain silicate crystals, and if the maturation time exceeds 20 days, the particle size of the silicate crystals may increase significantly to 1.0 to 4.0 nanometers, so it is not desirable. Can not do it.

In other words, when the maturation time is as described above, silicate crystals with a particle size of 0.2 to 0.6 nanometers that are ionized into an almost gaseous substance are obtained.

The mixing and heating step (S205) is a step of mixing and heating the silicate crystals obtained through the aging step (S203) with purified water, and 5,000 to 15,000 parts by weight of purified water per 100 parts by weight of the silicate crystals obtained through the aging step (S203). This is done by mixing parts by weight and heating to a temperature of 500 to 1000°C.

If the heating temperature is less than 500°C, the silicate crystals may not elute, and if the heating temperature exceeds 1000°C, the silicate crystals may evaporate and the recovery rate of the silicate crystals may be reduced.

The water-soluble silicic acid mixture prepared through the above process has a water solubility of more than 90%.

If the content of the water-soluble silicic acid mixture prepared through the above process is less than 0.1 part by weight, the antibacterial, antiviral and far-infrared radiation performance of the produced film is minimal, and if the content of the water-soluble silicic acid mixture exceeds 1 part by weight, the above effects While not significantly improved, physical properties such as transparency or mechanical strength of the film may be reduced.

At this time, the water-soluble silicic acid mixture may be applied after drying the water-soluble silicic acid mixture in an aqueous solution state, converting it to a powder state, and pulverizing it to 3 to 4㎛. In this case, 3 to 4 parts by weight are mixed compared to 100 parts by weight of the synthetic resin pellet. It is desirable to be

The drying step (S103) is a step of drying the mixture prepared through the raw material mixing step (S101), and the mixture prepared through the raw material mixing step (S101) is dried at a temperature of 45 to 60 ° C. for 5 to 7 hours. It is made by drying.

As moisture is removed through the drying step (S103), the water-soluble silicic acid mixture is applied to the surface of the synthetic resin pellet.

The forming step (S105) is a step of extruding the mixture dried through the drying step (S103) and forming it into a film. It is performed by extruding the mixture dried through the drying step (S103) with an extruder. After removing the moisture contained in the mixture through a provided hopper, the mixture from which the moisture has been removed is melted and extruded through an extruder equipped with a cylinder, screw, and die.

At this time, when the water-soluble silicate is applied after being converted to a powder state as described above and then pulverized to 3 to 4㎛, a process of injection molding using an injection machine may be applied in addition to the method of extruding with an extruder.

The cooling and winding step (S107) is a step of cooling and winding the molded product manufactured through the forming step (S105). The film molded product manufactured through the forming step (S105) is cooled to 40 to 60° C. by air cooling. It is then passed through a rotating roller to adjust the thickness and winding.

If the cooling temperature in the cooling and winding step is less than 40°C, it is not easy to control the thickness through the rotating roller. If the cooling temperature exceeds 60°C, the molded product may stick to the rotating roller or a fusion phenomenon may occur between films during winding. This is not desirable because it can occur.

Hereinafter, the manufacturing method of the antibacterial and antiviral film according to the present invention and the physical properties of the film manufactured by the manufacturing method will be described using examples.

<Preparation Example 1> Preparation of water-soluble silicic acid mixture

After removing foreign substances present on the surface of the silicate mineral, it was melted by heating in a furnace at a temperature of 1650°C for 13 hours, and then the molten silicate mineral was aged for 13 days to obtain silicate crystals, and 100 parts by weight of the obtained silicate crystals was added. After mixing with 10,000 parts by weight of purified water, it was heated to a temperature of 800°C to prepare a water-soluble silicic acid mixture in liquid form.

The water-soluble silicic acid mixture prepared in Preparation Example 1 was photographed with FE-SEM and shown in Figures 3 and 4 below. As shown in Figures 3 and 4 below, it can be seen that the water-soluble silicic acid mixture prepared through Preparation Example 1 of the present invention is in an amorphous state in which spherical silicon particles are randomly distributed.

<Comparative Example 1> Preparation of water-soluble silicic acid mixture

Proceed in the same manner as Preparation Example 1, but the molten silicate was aged for 8 hours to prepare a water-soluble silicic acid mixture.

<Comparative Example 2> Preparation of water-soluble silicic acid mixture

Proceed in the same manner as Preparation Example 1, but the molten silicate was aged for 5 hours to prepare a water-soluble silicic acid mixture.

<Comparative Example 3> Preparation of water-soluble silicic acid mixture

Proceed in the same manner as Preparation Example 1, but after mixing the silicate crystals with purified water, a water-soluble silicic acid mixture was prepared without heating.

The antibacterial properties of the water-soluble silicic acid mixtures prepared through Preparation Example 1 and Comparative Examples 1 to 3 were measured and shown in Table 1 below.

{However, antibacterial properties were tested using the paper disk diffusion assay as follows.

The test strains Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 15442 were each diluted to 10 ⁶ CFU/mL, and 100 μL of each diluted test strain was inoculated onto the MHA plate and applied using a sterilized cotton swab. Place a paper disk (8 mm) on the plate using sterilized forceps, absorb 50 μL of the water-soluble silicic acid (Na ₂ SiO ₃ ·10H ₂ O) of Preparation Example 1 and Comparison 1 to 3, and then cool to 37°C. Cultured for 24 hours in a set incubator. Distilled water was used as a control.}

Test Items Test result Initial concentration Concentration after 24 hours Bacterial reduction rate (%) caused by E. coli
antibacterial test control group 424 2863 - Manufacturing Example 1 424 One 99.8 Comparative Example 1 424 187 44.1 Comparative Example 2 424 205 48.3 Comparative Example 3 424 221 52.1 caused by Pseudomonas aeruginosa
Antibacterial test control group 437 2957 - Manufacturing Example 1 437 One 99.8 Comparative Example 1 437 177 40.5 Comparative Example 2 437 196 44.8 Comparative Example 3 437 214 48.9

As shown in Table 1, it can be seen that the water-soluble silicic acid mixture prepared through Preparation Example 1 of the present invention exhibits excellent antibacterial properties.

<Example 1>

100 parts by weight of synthetic resin (polyethylene) pellets were mixed with 0.4 parts by weight of the water-soluble silicic acid mixture prepared in Preparation Example 1, stirred at a speed of 100 rpm for 3 hours, dried at a temperature of 52°C for 6 hours, and the water-soluble silicic acid mixture was applied. After manufacturing the synthetic resin pellets, the moisture contained in the mixture is removed through a hopper provided in the extruder, and then the moisture-removed mixture is melt-extruded through an extruder equipped with a cylinder, screw, and die, and the extruded molded product is exposed to air. After cooling, it was passed through a rotating roller to adjust the thickness to 0.01 millimeter and then wound to produce an antibacterial and antiviral film.

<Comparative Example 1>

After removing the moisture contained in the synthetic resin (polyethylene) pellets through a hopper provided in the extruder, the moisture-removed mixture is melt-extruded through an extruder equipped with a cylinder, screw, and die, and the extruded molded product is cooled in air. It was then passed through a rotating roller to adjust the thickness to 0.01 millimeter and then wound to produce a film.

The antibacterial and antiviral properties of the antibacterial and antiviral film prepared in Example 1 and the film prepared in Comparative Example 1 were measured and shown in Figure 5 below.

(However, antibacterial properties were determined by packaging cream bread with manufactured film and photographing mold growth after 21 days at room temperature.)

As shown in Figure 5 below, it can be seen that the food packaged with the antibacterial and antiviral film prepared in Example 1 of the present invention did not develop mold even after 21 days.

In addition, the far-infrared radiation effect of the antibacterial and antiviral film prepared in Example 1 was requested by the Korea Far-Infrared Ray Society and is shown in a test report in Figure 6 below.

{However, the far-infrared radiation effect is expressed by the emissivity and radiation energy of the manufactured film, and the test method of KFIA-FI-1005 is used, and the measurement results are shown compared to BLACK BODY using a FT-IR Spectrometer at a temperature of 37℃. .}

As shown in Figure 6 below, it can be seen that the antibacterial and antiviral film prepared through Example 1 of the present invention has excellent far-infrared radiation effect.

Therefore, the method for producing an antibacterial and antiviral film according to the present invention not only exhibits excellent antibacterial and antiviral properties by containing a water-soluble silicic acid mixture, but also has excellent far-infrared radiation effect to suppress the growth of bacteria and mold, thereby suppressing the growth of bacteria and mold. Provides an antibacterial and antiviral film that has the effect of suppressing deterioration.

S101 ; Raw material mixing stage
S103 ; drying stage
S105 ; Molding stage
S107 ; Cooling winding step
S201 ; Heating and melting step
S203 ; Ripening stage
S205 ; Mixed heating step

Claims (8)

A raw material mixing step of mixing a water-soluble silicic acid mixture into synthetic resin pellets;
A drying step of drying the mixture prepared through the raw material mixing step;
A molding step of extruding the dried mixture through the drying step and forming it into a film; and
A method for producing an antibacterial and antiviral film, characterized in that it consists of a cooling and winding step of cooling and winding the molded product manufactured through the molding step,
The water-soluble silicic acid mixture includes a heating and melting step of heating and melting the silicate mineral; A maturing step of maturing the molten silicate mineral through the heating and melting step to obtain silicate crystals; and a mixing heating step of mixing purified water with the silicate crystals obtained through the aging step and heating them. In claim 1,
The raw material mixing step is a method of producing an antibacterial and antiviral film, characterized in that it is achieved by mixing 0.1 to 1 part by weight of a water-soluble silicic acid mixture with 100 parts by weight of synthetic resin pellets. In claim 1 or 2,
A method for producing an antibacterial and antiviral film, characterized in that the synthetic resin pellet is made of one selected from the group consisting of polyethylene, polypropylene, polyurethane, and acrylonitrile butadiene styrene copolymer. In claim 1,
The water-soluble silicic acid mixture is a method of producing an antibacterial and antiviral film, characterized in that it includes one or more selected from the group consisting of SiO ₃ , Na ₂ SiO ₃ and Na ₂ SiO ₃ ·10H ₂ O. delete In claim 1,
The heating and melting step is a method of producing an antibacterial and antiviral film, characterized in that the silicate mineral is heated at a temperature of 1500 to 2000 ° C. for 10 to 20 hours. In claim 1,
A method for producing an antibacterial and antiviral film, characterized in that the ripening step is performed for 10 to 20 days. In claim 1,
The mixing heating step is performed by mixing 5000 to 15000 parts by weight of purified water with 100 parts by weight of the silicate crystals obtained through the aging step and heating to a temperature of 500 to 1000° C. A method of producing an antibacterial and antiviral film.