Method for manufacturing biodegradable protective film

Abstract

The present invention relates to a method for manufacturing a biodegradable protective film. More specifically, the present invention relates to a method for manufacturing a biodegradable protective film, in which a PCI technique is used to enable processing at a low temperature, and damage to organic materials can be minimized.

Description

Method for manufacturing biodegradable protective film

[0001] The present invention relates to a method for manufacturing a biodegradable protective film. More specifically, the present invention relates to a method for manufacturing a biodegradable protective film that utilizes the PCI technique, enables low-temperature processing, and minimizes damage to organic matter.

[0002]

[0003] Conventional biodegradable coatings have evolved in various directions, utilizing both organic and inorganic materials. Inorganic materials, such as SiO2, offer the advantages of long-term biodegradability and low water and oxygen permeability. However, they also require heat treatment at temperatures exceeding 500°C.

[0004] This heat treatment process cannot be used with biological materials such as proteins and enzymes, as well as with general plastics, so additional processes such as transferring the film after manufacturing are required.

[0005] Organic materials, such as wax and polymers like PLGA, have lower water and oxygen permeability than inorganic materials, but they offer the advantage of solution processing using organic solvents. However, the use of organic solvents inevitably leads to the formation of numerous porous structures during the drying process, which not only reduces film density but also increases water and oxygen permeability.

[0006]

[0007] The present invention aims to provide a method for manufacturing a biodegradable protective film that can be processed at a low temperature and minimizes damage to organic matter compared to existing biodegradable protective film manufacturing processes.

[0008]

[0009] A method for manufacturing a biodegradable protective film may include a step of mixing wax and oil to prepare a mixture, a step of mixing the mixture with a surfactant to prepare an emulsion using a PIC technique, and a step of drying the emulsion to prepare a thin film.

[0010] The above wax may be a hydrocarbon series wax.

[0011] The above oil may be a hydrocarbon oil.

[0012] The method for manufacturing a biodegradable protective film may further include a step of cooling the manufactured emulsion.

[0013] The size of the above emulsion may be from ㎛ to ㎚.

[0014] The method for manufacturing a biodegradable protective film may further include a step of heat treating the emulsion.

[0015]

[0016] The method for manufacturing a biodegradable protective film of the present invention can be performed at low temperatures, thereby minimizing damage to such organic materials. Furthermore, the present invention provides a biodegradable protective film that can be used to protect organic materials, including proteins and enzymes.

[0017]

[0018] Figure 1 is a flowchart showing a method for manufacturing a biodegradable protective film according to one embodiment of the present invention.

[0019] Figure 2 illustrates the contact angle of an emulsion manufactured according to one embodiment of the present invention.

[0020] Figure 3 is a graph showing the size of the contact angle of an emulsion manufactured according to one embodiment of the present invention.

[0021] FIG. 4 illustrates an SEM image of a film manufactured according to one embodiment of the present invention.

[0022] FIG. 5 illustrates SEM images of films having different emulsion sizes manufactured according to one embodiment of the present invention.

[0023] FIG. 6 illustrates the contact angle of an emulsion to which silica particles are added according to one embodiment of the present invention.

[0024] FIG. 7 is a graph showing the contact angle of an emulsion to which silica particles are added according to one embodiment of the present invention.

[0025] Figure 8 illustrates the current value of a film that has undergone heat treatment according to one embodiment of the present invention.

[0026]

[0027] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention.

[0028] However, the following description is not intended to limit the present invention to a specific embodiment, and when explaining the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description is omitted.

[0029] The terminology used herein is merely for the purpose of describing specific embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In the present invention, it should be understood that the terms "comprise" or "have" indicate the presence of a feature, number, step, operation, component, or combination thereof described in the specification, but do not preclude the presence or addition of one or more other features, numbers, steps, operations, components, or combinations thereof.

[0030] Additionally, terms including ordinal numbers, such as "first," "second," etc., which will be used hereinafter, may be used to describe various components, but these components are not limited by these terms. These terms are used solely to distinguish one component from another. For example, without departing from the scope of the present invention, a first component could be referred to as a second component, and similarly, a second component could also be referred to as a first component.

[0031] Additionally, when it is said that a component is "formed on" or "laminated on" another component, it should be understood that it may be formed or laminated directly on the entire surface or one side of the other component, but there may also be other components present in between.

[0032] The method for manufacturing a biodegradable protective film of the present invention may include a step of mixing wax and oil to prepare a mixture, a step of mixing the mixture with a surfactant to prepare an emulsion using a PIC technique, and a step of drying the emulsion to prepare a thin film.

[0033] The above PIC (Phase inversion composition) technique may be a technique of adding water at a constant rate to a mixture of wax, oil, and surfactant.

[0034] The above-mentioned Phase Inversion Composition (PIC) technique can be used to produce micro- and nano-scale emulsions. These emulsions are highly scalable and can be used as organic / inorganic hybrid materials by mixing inorganic materials. The resulting hybrid materials can inhibit water and oxygen permeation.

[0035] The above nano-unit emulsion may have a size of 50 to 100 nm.

[0036] The above micro-unit emulsion may have a size of 1 to 10 μm.

[0037] The steps for drying the above emulsion are specifically as follows. The emulsion manufactured through the PIC technique may be applied onto a substrate by drop casting and then dried under conditions of room temperature and pressure.

[0038] The method for manufacturing a biodegradable protective film of the present invention may further include a step of cooling the manufactured emulsion.

[0039] The size of the emulsion particles can be changed through the step of cooling the emulsion manufactured above. The faster the cooling of the manufactured emulsion, the smaller the emulsion particle size can be.

[0040] The method for manufacturing a biodegradable protective film of the present invention may further include a step of mixing silica nanoparticles into the prepared emulsion. The silica nanoparticles may be added and mixed in an amount of 3 to 7% relative to the total weight of the prepared emulsion.

[0041] When silica nanoparticles are mixed into the emulsion manufactured above, performance can be improved.

[0042] The method for manufacturing a biodegradable protective film of the present invention may further include a step of heating the manufactured thin film at 40 to 60°C. The performance of the film can be improved through heating the thin film.

[0043] Specifically, the film's resistance to water penetration can be improved by heating the thin film.

[0044] Biodegradable polymer films can have different density and film quality depending on the size of the emulsion and the manufacturing process.

[0045] In general, in the case of a solution process used to manufacture a polymer film, a porous structure may be formed in the polymer during the evaporation process of the organic solvent.

[0046] When wax is dissolved in ethanol and processed as a solution process, a problem may arise in which a porous structure is formed in the polymer, thereby lowering the density and film quality of the film.

[0047] Nanoemulsions have a characteristic larger interface than microemulsions. Therefore, nanoemulsions can more effectively block water and oxygen permeation.

[0048] The above wax may include a hydrocarbon series wax. Specifically, the wax may be at least one selected from candelilla wax and beeds wax.

[0049] The above oil may include a hydrocarbon wax. Specifically, the oil may be at least one selected from sunflower oil and jojoba oil.

[0050] According to one embodiment of the present invention, the ratio of the wax and oil may be 80 to 100 parts by weight of wax and 0 to 20 parts by weight of oil per 100 parts by weight of the mixture of wax and oil. However, the present invention is not limited thereto.

[0051] The surfactant may be prepared by mixing Span 80 (4.3) and Tween 80 (15). Specifically, the surfactant may be a surfactant having an HLB value of 14. The surfactant may be a mixture of Span 80 (4.3) and Tween 80 (15) in a weight ratio of 7 to 9: 91 to 93, respectively.

[0052] A method for manufacturing a biodegradable protective film according to one embodiment of the present invention is specifically as follows.

[0053] A mixture of wax and oil is heated. Thereafter, the mixture is mixed with a surfactant. The ratio of the mixture of wax and oil and the surfactant may be from 1:1 to 1:0. For example, the ratio of the mixture of wax and oil and the surfactant may be 1:0, 1:0.2, 1:0.4, 1:0.4, 1:0.6, 1:0.8, and 1:1.

[0054] Afterwards, water is added at a rate of 1 ml / min to the material mixed with the above mixture and surfactant. After the above process is performed for 30 minutes (min), the mixture is cooled in cold water to produce an emulsion.

[0055] The size of the above emulsion may be from ㎛ to ㎚. The size of the emulsion formed may vary depending on the cooling time in the cold water. If the cooling time in the cold water is short, a nanoemulsion may be formed, and if the cooling time in the cold water is long, a microemulsion may be formed.

[0056] The step of drying the emulsion according to one embodiment of the present invention to produce a thin film may be to dry the produced emulsion under conditions of room temperature and normal pressure.

[0057] According to one embodiment of the present invention, a process of adding silica nanoparticles after heating a mixture of wax and oil may be further included. A method for manufacturing a biodegradable protective film according to one embodiment of the present invention may further include a step of heat-treating an emulsion.

[0058] Conventional processes have the disadvantage of requiring post-processing, such as heat treatment, to be performed at high temperatures of 100°C or higher due to the need to consider factors such as the melting point of polymer materials. According to the present invention, the properties of a biodegradable film can be controlled by adjusting the mixing ratio of wax, oil, and surfactant. Furthermore, post-processing can be performed at relatively low temperatures. When the post-processing process was performed, the density of the biodegradable polymer film increased, and the interface between particles was reduced. Accordingly, the post-processing process has the effect of reducing water and oxygen permeation.

[0059] The polymer in emulsion form of the present invention can be relatively easily mixed with other organic / inorganic materials. According to one embodiment of the present invention, the organic / inorganic material may be silica nanoparticles.

[0060] According to one embodiment of the present invention, the time required for biodegradation to occur was increased when silica nanoparticles were mixed. Furthermore, the effect of reducing water and oxygen permeation was also observed.

[0061] In one embodiment of the present invention, a polymer film may be manufactured by mixing with CNT.

[0062] In one embodiment of the present invention, the biodegradable film can be used to protect organic materials such as protein enzymes.

[0063] The biodegradable protective film of the present invention can take advantage of its ability to biodegrade over a certain period of time. This makes it suitable for use as a protective coating for various enzyme-based sensors and technologies. It can also be utilized in drug delivery systems.

[0064]

[0065] Manufacturing Example 1.

[0066] 1) Manufacture of surfactants

[0067] A surfactant with an HLB of 14 is prepared using Span 80 (4.3): 9% and Tween 80 (15): 91%.

[0068] 2) Preparation of hydrocarbon wax and oil

[0069] Candelilla wax was prepared for the wax, and sunflower oil was prepared for the oil.

[0070] 3) Mixing of wax and oil

[0071] For the total weight of the mixture of wax and oil, mix in a ratio of 80% wax and 20% oil.

[0072] 4) Preparation of emulsion

[0073] Prepare 1g of a mixture of wax and oil and heat it at 80℃. Then, mix the mixture with the surfactant of 1) in a 1:1 ratio. Then, add 18ml of water at a rate of 1ml / min. Mix for approximately 30 minutes and cool in cold water to prepare an emulsion.

[0074]

[0075] Manufacturing example 2.

[0076] Prepare 1g of a mixture of wax and oil and heat it. Then, add 3wt% of silica nanoparticles based on the total weight of the mixture. Then, mix the surfactant of 1) in a 1:1 ratio. Then, add 18ml of water at a rate of 1ml / min. After mixing for approximately 30 minutes, cool it in cold water to prepare an emulsion.

[0077]

[0078] Experimental Example 1. Comparison of emulsion particle size according to the ratio of surfactant and mixture.

[0079] In the above manufacturing example 1, when the cooling rate with cold water was set differently, the size of the emulsion manufactured and the surface difference of the film finally manufactured were compared.

[0080] Figure 2 illustrates the contact angle of an emulsion manufactured according to one embodiment of the present invention.

[0081] Figure 3 is a graph showing the size of the contact angle of an emulsion manufactured according to one embodiment of the present invention.

[0082] Referring to Figures 2 and 3, when the ratio of the mixture of wax and oil to the surfactant was 1:1, the contact angle was low at 10.2, but when no surfactant was added, it showed the highest value at 92.4.

[0083] FIG. 4 illustrates an SEM image of a film manufactured according to one embodiment of the present invention.

[0084] Referring to Fig. 4, there was no significant difference in the surface film quality of dried emulsions prepared according to different ratios of surfactant and mixture.

[0085] FIG. 5 illustrates SEM images of films having different emulsion sizes manufactured according to one embodiment of the present invention.

[0086] Referring to Figure 5, it can be confirmed that the density of the emulsion film manufactured using the PIC technique is higher than that of the emulsion film manufactured by dissolving in an organic solvent. In addition, it can be confirmed that the particle grains of the film manufactured using the nanoemulsion are larger than those of the film manufactured using the microemulsion.

[0087] FIG. 6 illustrates the contact angle of an emulsion to which silica particles are added according to one embodiment of the present invention.

[0088] FIG. 7 is a graph showing the contact angle of an emulsion to which silica particles are added according to one embodiment of the present invention.

[0089] Referring to Figures 6 and 7, it can be confirmed that the hydrophilic and hydrophobic properties of the emulsion to which silica particles were added according to Manufacturing Example 2 changed. In addition, it can be confirmed that when silica particles are added to the emulsion, there is no significant difference in the SEM image, but there is a tendency for some parts to change to hydrophobic properties.

[0090] Figure 8 illustrates the current value of a film that has undergone heat treatment according to one embodiment of the present invention.

[0091] Referring to Figure 8, it can be confirmed that the film quality is improved through heat treatment. Furthermore, post-processing (heat treatment) is possible at a fertilizer-low temperature of approximately 50°C, and it can be confirmed that the water permeability is reduced after heat treatment.

Claims

1. A step of preparing a mixture by mixing wax and oil; A step of preparing an emulsion through the PIC technique by mixing the above mixture with a surfactant; and Comprising a step of drying the above emulsion to produce a thin film, Method for manufacturing biodegradable protective film.

2. In paragraph 1, The above wax is a hydrocarbon series wax, Method for manufacturing biodegradable protective film.

3. In paragraph 1, The above oil is a hydrocarbon oil. Method for manufacturing biodegradable protective film.

4. In paragraph 1, Further comprising a step of cooling the manufactured emulsion, Method for manufacturing biodegradable protective film.

5. In paragraph 1, The size of the above emulsion is 50 nm to 100 μm, Method for manufacturing biodegradable protective film.

6. In paragraph 1, Further comprising a step of heat treating the above emulsion, Method for manufacturing biodegradable protective film.

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