KR102571933B1 - Antifouling member using porous needle structure and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an antifouling member using a porous needle structure and a method for manufacturing the antifouling member, wherein the antifouling material is continuously released through the connected pores of the porous structure by controlling the hydraulic pressure of the antifouling fluid containing the antifouling material, and the amount of the antifouling material is continuously released. It relates to an antifouling member that removes surface contaminants by controlling and a method for manufacturing the antifouling member. According to the antifouling member of the present invention, by continuously supplying and releasing the antifouling material, it is possible to fundamentally block the generation and proliferation of microorganisms, and it is possible to control the emission amount of the antifouling material, thereby saving the antifouling material and enhancing the antifouling effect. there is.

Description

Antifouling member using porous needle structure and manufacturing method thereof

The present invention relates to an antifouling member using a porous needle structure and a method for manufacturing the antifouling member, wherein the antifouling material is continuously released through the connected pores of the porous structure by controlling the hydraulic pressure of the antifouling fluid containing the antifouling material, and the amount of the antifouling material is continuously released. It relates to an antifouling member that removes surface contaminants by controlling and a method for manufacturing the antifouling member.

In general, microorganisms including bacteria proliferate after being generated in stagnant water or fluids, and are largely divided into fungi, bacteria, protozoa, algae, and the like, and live in fluids.

Bacteria proliferate and form a protective film when self-reproduction is disadvantageous, and this protective film is called a biofilm or bacterial biofilm. When bacteria form a biofilm on internal tissues of the human body or medical devices, there is a problem in that the antibacterial effect of antibiotics and chemicals is lowered. In addition, when formed on the hull, there is a problem of degrading the performance of the ship and increasing the fuel consumption.

Conventionally, a surface coating method or a chemical grafting method has been mainly used to inhibit the generation and proliferation of microorganisms. The surface coating method has a disadvantage in that the coating layer is peeled off during long-term operation, and the chemical grafting method has difficult reaction conditions and difficulty in large-area application. In addition, microorganisms such as bacteria easily have resistance to chemicals, so there is a problem in that the antifouling function is reduced.

Recently, a method of adding an antifouling paint or an antifouling agent into a fluid or irradiating a radiation source such as ultraviolet rays has been used to suppress the generation and proliferation of microorganisms. However, most antifouling paints or antifouling agents contain toxic tri-butyl tin, cuprous oxide (CuO), and various organic antifouling agents to kill microorganisms, so that toxic antifouling agents are released into the water from the surface of the paint. There is a problem with release. In addition, the method of adding antifouling paint or antifouling agent or irradiating a radiation source such as ultraviolet rays has a problem in that the proliferation of microorganisms cannot be fundamentally prevented.

In order to solve this problem, Korean Patent Registration No. 10-1994503 provides an adhesive tape for preventing the attachment of aquatic organisms. It can express good adhesiveness even in water, has good mechanical properties, is easy to peel, and can maintain the antifouling effect over a long period of time, effectively preventing the attachment of aquatic organisms. However, the anti-fouling adhesive tape of Korean Patent Registration No. 10-1994503 has a continuous anti-fouling effect only while the anti-fouling layer contains the anti-fouling agent, and when the anti-fouling agent is exhausted, the anti-fouling effect decreases, so the adhesive tape must be removed. There is a problem with

Under this background, the present inventors tried to develop an antifouling member capable of fundamentally preventing the generation and proliferation of microorganisms by controlling the amount of antifouling material released while continuously releasing the antifouling material. As a result, by controlling the hydraulic pressure of the antifouling fluid storage layer communicating with the porous needle structure layer to form a moving path of the antifouling fluid, the antifouling material is injected into the pores of the porous needle structure layer to enable continuous release of the antifouling material, The present invention was completed by discovering that the amount of emission of the material can be controlled.

An object of the present invention is an antifouling fluid storage layer; a porous needle structure layer formed by being laminated on the antifouling fluid storage layer; and a driving unit communicating with the antifouling fluid storage layer. The antifouling fluid storage layer and the porous needle structure layer communicate with each other to form a movement path of the antifouling fluid, and the driving unit controls the hydraulic pressure of the antifouling fluid storage layer.

Another object of the present invention is to laminate a porous needle structure layer on the antifouling fluid storage layer; communicating the driving unit to the antifouling fluid storage layer; and controlling a hydraulic pressure by introducing an antifouling fluid into the antifouling fluid storage layer.

Another object of the present invention is to laminate a porous needle structure layer on the antifouling fluid storage layer; communicating the driving unit to the antifouling fluid storage layer; and controlling a hydraulic pressure by introducing an antifouling fluid into the antifouling fluid storage layer.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

According to the antifouling member of the present invention, by continuously supplying and releasing the antifouling fluid containing the antifouling material, it is possible to fundamentally block the generation and proliferation of microorganisms.

According to the antifouling member of the present invention, the release amount of the antifouling fluid containing the antifouling material can be controlled, so that the antifouling material can be saved and the antifouling effect can be enhanced.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a view showing the operating principle of an antifouling member according to an embodiment of the present invention.
2 is a cross-sectional view of a porous needle structure layer manufactured according to an embodiment of the present invention.
3a and 3b show that bacteria on the surface are removed by adjusting the pH of the porous needle structure layer.
Figure 4 shows the removal of bacteria on the surface by controlling the temperature of the porous needle structure layer.
5 shows that the magnitude of the pressure applied to the porous needle structure layer may vary depending on the size and shape of a plurality of pores.
6A shows an example of applying the antifouling member according to an embodiment of the present invention to an indwelling urinary catheterization.
6B shows an example in which contaminants are removed by applying the antifouling member according to an embodiment of the present invention to an indwelling urinary catheter.
7A and 7B show an example in which contaminants are removed by pneumatically changing the surface of the antifouling member according to an embodiment of the present invention.
Figure 8 shows the antifouling effect according to the needle shape and needle spacing of the porous needle structure layer according to an embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes can be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all changes, equivalents or substitutes to the embodiments are included within the scope of rights.

The terms used in the examples are used for descriptive purposes only and should not be construed as intended to limit the scope of rights. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

In addition, in the description with reference to the accompanying drawings, the same reference numerals are given to the same components regardless of reference numerals, and overlapping descriptions thereof will be omitted. In describing the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description will be omitted.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

1 shows the structure and operating principle of an antifouling member according to an embodiment of the present invention.

Referring to FIG. 1 , an antifouling member according to an embodiment of the present invention includes an antifouling fluid storage layer; a porous needle structure layer formed by being laminated on the antifouling fluid storage layer; and a driving unit communicating with the antifouling fluid storage layer. The antifouling fluid storage layer and the porous needle structure layer communicate with each other to form a movement path of the antifouling fluid, and the driving unit controls the hydraulic pressure of the antifouling fluid storage layer.

As used herein, the term "antifouling" means a property of preventing contamination, and "antifouling fluid" means a gas or liquid containing an antifouling material. The antifouling fluid may include any one antifouling material selected from peptides, hydrophilic materials, zwitterionic materials, and hydrophobic materials.

The antifouling fluid storage layer serves as a reservoir for collecting and confining the antifouling fluid. In addition, the antifouling fluid storage layer serves as a movement passage through which the antifouling fluid flows into the porous needle structure layer formed by being stacked on the antifouling fluid storage layer. The antifouling fluid storage layer is made of a porous material and has a structure in which fluid can continuously flow into the storage layer impregnated with the antifouling material. The antifouling fluid storage layer has a low modulus, and surface deformation may occur due to external force.

The antifouling fluid storage layer is formed in communication with a porous needle structure layer formed by being laminated on the antifouling fluid storage layer. The antifouling fluid storage layer is formed by communicating with a side surface of the bottom window layer with a driving unit capable of adjusting the hydraulic pressure of the antifouling fluid. The driving unit formed in communication may continuously supply the antifouling material to the antifouling fluid storage layer.

The antifouling fluid storage layer may include a microfluidic chip.

As used herein, the term “microfluidic chip” has a function of simultaneously performing various experimental conditions by flowing a fluid through a microfluidic channel. Specifically, microchannels are made using a substrate (or chip material) such as plastic, glass, or silicon, and a fluid (eg, liquid sample) is moved through these channels, and then the sample is placed in a chamber within the microfluidic chip. Separation, mixing of cells, synthesis, quantitative analysis, observation of cell proliferation, etc. are possible. Preferably, a microfluidic chip having an antifouling effect by flowing an antifouling fluid through a microfluidic channel is included in the antifouling fluid storage layer, so that the antifouling material can be continuously released and the antifouling effect can be enhanced. The pump connected to the microfluidic chip can continuously supply the antifouling material and continuously release the antifouling material to the outside. In addition, the flow rate (ml/min) of the antifouling fluid flowing through the microfluidic channel can be controlled by using a pump to control the release amount of the antifouling material.

The antifouling fluid storage layer is formed of a flexible and stretchable polymer. This is to allow the device to be flexibly attached according to the shape of the surface of the ship or marine facility when the device is installed on a ship or marine facility, and to continuously release the antifouling material and control the amount of the emission. The antifouling fluid storage layer is deformed by an external fluid flow, and the antifouling material impregnated in the storage layer is continuously discharged to the outside through the porous needle structure layer by the pressure caused by the surface deformation.

The antifouling fluid storage layer may be made of any one of polydimethylsiloxane (PDMS), ecoflex, Triton X, and hydrogel, and imparts flexibility to the antifouling fluid storage layer. The material is not limited to this.

2 is a cross-sectional view of a porous needle structure layer manufactured according to an embodiment of the present invention.

The porous needle structure layer may include a plurality of pores, the plurality of pores may be formed in communication, and the plurality of communicated pores may form a movement path of the antifouling material. The plurality of pores are connected to each other to form a physical structure, to collect a large amount of antifouling material, and to provide a physical space in which the antifouling material can continuously flow. The antifouling material may be continuously released through the porous needle structure layer.

The needle structure of the porous needle structure layer may have a cone shape or a column shape in which tips capable of penetrating microorganisms are formed. However, it is not limited thereto as long as it has a shape capable of penetrating contaminants such as microorganisms.

As used herein, the term "microorganism" refers to a collection of organisms that exhibit very diverse functions in terms of genetic, physiological, biochemical, and ecological aspects, including protists, fungi, bacteria, archaea, and viruses.

The porous needle structure layer is composed of polyethersulfone (PES), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), poly N-isopropylacrylamide (PNIPAM), polymetha It may be made of any one of acrylic acid (polymethacrylic acid; PMAA), methyl cellulose, and chitosan.

Preferably, the porous needle structure layer includes polyethersulfone (PES) and polyvinylpyrrolidone (PVP), and may further include potassium perchlorate (KClO ₄ ) and dimethylacetamide (DMA) there is.

The porous needle structure layer is composed of polyethersulfone (PES), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), poly N-isopropylacrylamide (PNIPAM), polymetha It may be made of any one of acrylic acid (polymethacrylic acid; PMAA), methyl cellulose, and chitosan.

Preferably, the porous needle structure layer includes polyethersulfone (PES) and polyvinylpyrrolidone (PVP), and may further include potassium perchlorate (KClO4) and dimethylacetamide (DMA). .

The porous needle structure layer includes 10 to 20 parts by weight of polyethersulfone (PES), 1 to 10 parts by weight of polyvinylpyrrolidone (PVP), 1 to 10 parts by weight of potassium perchlorate (KClO4), And dimethylacetamide (dimethylacetamide, DMA) may be included in 70 to 90 parts by weight. Preferably, polyethersulfone (PES) may be included in 15 to 17 parts by weight. Preferably, polyvinylpyrrolidone (PVP) may be included in 2 to 3 parts by weight. Preferably, potassium perchlorate (KClO4) may be included in 1 to 5 parts by weight. Preferably, dimethylacetamide (DMA) may be included in 75 to 85 parts by weight.

The porous needle structure layer may release antifouling material according to pH or temperature change.

Referring to FIG. 3A, the porous needle structure layer made of hydrogel containing gold nanoparticles (Au nanoparticles) having antifouling or antibacterial properties releases gold nanoparticles in response to pH change, thereby removing S. aureus bacteria on the surface. do.

Referring to FIG. 3B, the porous needle structure layer made of polymethyl methacrylate containing an antimicrobial agent having antifouling or antibacterial properties releases the antimicrobial agent in response to a pH change, so that S. epidermidis bacteria on the surface Removed.

Referring to FIG. 4, the porous needle structure layer made of polyisopropylacrylamide expands in volume with temperature to release quaternary ammonium salts to remove contaminants on the surface.

The driving unit may communicate with the antifouling fluid storage layer and adjust the hydraulic pressure of the antifouling fluid storage layer. The driving unit may serve to fill the antifouling fluid storage layer with the antifouling fluid. In addition, the driving unit may adjust the amount of release of the antifouling material by adjusting the hydraulic pressure of the antifouling fluid storage layer.

The driving unit may vary the pressure applied to the antifouling fluid storage layer according to the size and shape of the plurality of pores of the porous needle structure layer.

Referring to FIG. 5 , it is shown that the pressure applied to the porous needle structure layer may vary depending on the shape and size of a plurality of pores.

The following equation is an equation showing that the magnitude of the pressure may vary depending on the size and shape of a plurality of pores. Referring to FIG. 5, the total compression energy of a unit volume in the internal system of the boundaries of Lx, Ly, and Lz means the sum of the compression energies of the fluid and the compression energies of the pores minus the internal energy between the fluid and the particles.

pV: Compression energy within a unit volume.

p ^f V ^f : means the compressive energy of the fluid within a unit volume.

p ^r V ^r : Compression energy of pores in unit volume.

γ ^fr Ω ^fr : Internal energy between fluid and particles.

(r: porous medium, f: single fluid, p: pressure in unit volume, V: volume in unit volume, p ^r : pressure of particles in unit volume, V ^r : volume of particles in unit volume, p ^f : unit volume of fluid pressure, v ^f : volume of unit volume, γ ^fr : surface tension, Ω ^fr : surface area between fluid and particle)

An antifouling member according to another embodiment of the present invention includes an antifouling fluid storage layer; a porous needle structure layer formed by being laminated on the antifouling fluid storage layer; and a driving unit communicating with the antifouling fluid storage layer, wherein the antifouling fluid storage layer and the porous needle structure layer communicate with each other to form a movement path of the antifouling fluid, and the driving unit controls hydraulic pressure of the antifouling fluid storage layer. It may further include a transducer that controls and transmits ultrasonic waves to the antifouling fluid storage layer to generate fine vibrations. The transducer can control the emission of the antifouling material by generating microvibrations.

Looking at the process of controlling the release of the antifouling material, the antifouling fluid is filled in the antifouling fluid storage layer and the hydraulic pressure of the antifouling fluid storage layer is increased so that the antifouling fluid can flow into a plurality of communicated pores of the porous structure. When contaminants are deposited on the surface of the porous needle structure layer, the antifouling fluid may be discharged by increasing the hydraulic pressure of the antifouling fluid storage layer to remove the contaminants. When contaminants on the surface of the porous needle structure layer are not deposited, the antifouling fluid may be filled in the antifouling fluid storage layer by lowering the hydraulic pressure of the antifouling fluid storage layer.

In the method for manufacturing a porous needle structure layer according to another embodiment of the present invention, 10 to 20 parts by weight of polyethersulfone (PES), 1 to 10 parts by weight of polyvinylpyrrolidone (PVP), potassium perchlorate (KClO ₄ ) mixing 1 to 10 parts by weight and 70 to 90 parts by weight of dimethylacetamide (DMA); Putting the mixed solution into a stirrer and mechanically stirring it for 10-12 hours; and forming a porous structure by pouring the stirred solution into a mold and hardening it. Preferably, polyethersulfone (PES) may be included in 15 to 17 parts by weight. Preferably, polyvinylpyrrolidone (PVP) may be included in 2 to 3 parts by weight. Preferably, potassium perchlorate (KClO ₄ ) may be included in 1 to 5 parts by weight. Preferably, dimethylacetamide (DMA) may be included in 75 to 85 parts by weight. The content of potassium perchlorate (KClO ₄ ) affects the porous structure, and as the content of potassium perchlorate (KClO ₄ ) increases, a more dense porous structure can be formed. The curing may be performed by a UV curing method. [Table 1] shows the pore size according to the content of potassium perchlorate (KClO ₄ ).

[Table 1] Pore size according to the content of potassium perchlorate (KClO ₄ )

A method of manufacturing an antifouling member according to another embodiment of the present invention includes laminating a porous needle structure layer on an antifouling fluid storage layer; communicating the driving unit to the antifouling fluid storage layer; and controlling a hydraulic pressure by introducing an antifouling fluid into the antifouling fluid storage layer. The manufacturing method of the antifouling member according to another embodiment of the present invention may further include connecting a transducer to the antifouling fluid storage layer.

According to another embodiment of the present invention, a method of removing contaminants is provided by utilizing the antifouling member manufactured by the method of manufacturing the antifouling member. According to the contaminant removal method of the present invention, the proliferation and occurrence of microorganisms can be inhibited by removing contaminants attached to the surface of the porous needle structure layer and preventing access of contaminants adjacent to the surface of the porous needle structure layer.

The antifouling member manufactured according to the present invention is an intermittent catheter, a Foley catheter, a tracheal tube, a central venous catheter, a Swan-hepatic catheter Ganz catheter), embryo transfer catheter, umbilical cord catheter, Tuohy-Borst adapter, and intrauterine catheter. In addition, the antifouling member manufactured according to the present invention can be used for artificial joints, implants, ships, and offshore structures.

Referring to FIGS. 6A and 6B , it is shown that the antifouling member manufactured according to an embodiment of the present invention is applied to an indwelling catheterization to remove contaminants. By applying surface deformation to the inside of the indwelling catheter with hydraulic pressure, contaminants on the surface of the indwelling catheter are removed, and the indwelling catheter can be used repeatedly. When the surface strain of the indwelling catheter is 30 to 35%, 70 to 80% of contaminants on the surface of the indwelling catheter can be removed.

Referring to FIGS. 7A and 7B , it is shown that contaminants on the surface can be separated and removed by deforming the surface of the antifouling member manufactured according to an embodiment of the present invention using pneumatic pressure. When the surface strain is 1 to 20%, up to 70 to 90% of contaminants on the surface can be removed. When a pneumatic pressure of 1KPa to 20kPa is applied to the porous needle structure layer made of a flexible material, up to 100% of contaminants can be removed.

Referring to FIG. 8 , the needle shape of the porous needle structure layer may be a shape mimicking the surface nanostructure of cicada wings. It is preferable that the needles of the porous needle structure layer have a height of 300 nm or more, an upper diameter of 50 nm or less, and a lower diameter of 200 nm or more. In addition, as the interval between the needles of the porous needle structure layer is narrowed, the antifouling effect may be improved.

Hereinafter, the present invention will be described in more detail through examples. The following examples are described for the purpose of illustrating the present invention, but the scope of the present invention is not limited thereto.

<Example 1: Preparation of porous needle structure layer>

15 to 17 parts by weight of polyethersulfone (PES), 2 to 3 parts by weight of polyvinylpyrrolidone (PVP), 1 to 5 parts by weight of potassium perchlorate (KClO ₄ ), and dimethylacetamide (DMA) It was mixed and cured at 75 to 85 parts by weight. Accordingly, the average size of pores according to the content of the components of the porous needle structure layer was measured. As shown in [Table 1], a more dense structure was formed as the content of potassium perchlorate (KClO ₄ ) increased.

<Example 2: Manufacturing of an antifouling member comprising a porous needle structure layer>

A porous needle structure layer was prepared according to Example 1. The antifouling fluid storage layer is made of polydimethylsiloxane (PDMS), silicone oil, organogel, ecoflex, Triton X, and hydrogel. made in one. The drive unit was communicated with the antifouling fluid storage layer, and a porous needle structure layer was laminated on the antifouling fluid storage layer.

<Experimental example. Antifouling test of antifouling member including porous needle structure layer>

In order to test the antifouling effect of the antifouling member prepared according to Example 2, the biofilm and the barnacle were grown for a certain period of time, and the antifouling test by surface deformation was performed while repeatedly applying pressure 30 times for 3 minutes, respectively. proceeded.

As a result, it was confirmed that up to 70 to 90% of contaminants on the surface can be removed when the surface strain is 1 to 20%, as shown in FIG. 7a below.

In addition, the biofilm of the antifouling member prepared according to Example 2 was grown for a certain period of time, and an antifouling test by surface deformation was conducted while repeatedly stretching each strain 30 times for 3 minutes.

As a result, it was confirmed that up to 70 to 90% of contaminants on the surface can be removed when the surface strain is 1 to 20%, as shown in FIG. 7B below.

Referring to FIG. 8, the height of the needles of the porous needle structure layer is 300 nm or more, the upper diameter is 50 nm or less, and the lower diameter is 200 nm or more. It was confirmed that indicated

As described above, although the embodiments have been described with limited drawings, those skilled in the art can apply various technical modifications and variations based on the above. For example, even if the described techniques are performed in a different order from the described method, and/or the described components are combined or combined in a different form than the described method, or substituted or replaced by other components or equivalents. Appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents of the claims are within the scope of the following claims.

Claims (7)

an antifouling fluid storage layer;
a porous needle structure layer formed by being laminated on the antifouling fluid storage layer; and
a driving unit communicating with the antifouling fluid storage layer;
including,
The porous needle structure layer includes a plurality of pores and the plurality of pores are in communication,
The antifouling fluid storage layer and the porous needle structure layer communicate with each other through a plurality of pores to form a movement path of the antifouling fluid,
The driving unit controls the hydraulic pressure of the antifouling fluid storage layer,
The porous needle structure layer includes polyethersulfone (PES), polyvinylpyrrolidone (PVP), potassium perchlorate (KClO ₄ ), and dimethylacetamide (DMA),
Absence of antifouling.
According to claim 1,
The antifouling fluid storage layer further comprises a microfluidic chip, the antifouling member.
According to claim 1 or 2,
The antifouling fluid storage layer may be any one of polydimethylsiloxane (PDMS), silicone oil, organogel, ecoflex, Triton X, and hydrogel. An antifouling member made of one piece.
According to claim 1 or 2,
The antifouling fluid is an antifouling member comprising any one of antifouling materials selected from peptides, hydrophilic materials, zwitterionic and hydrophobic materials.
delete laminating a porous needle structure layer on the antifouling fluid storage layer;
communicating a driving unit to the antifouling fluid storage layer; and
controlling a hydraulic pressure by introducing an antifouling fluid into the antifouling fluid storage layer;
including,
The porous needle structure layer includes a plurality of pores and the plurality of pores are in communication,
The antifouling fluid storage layer and the porous needle structure layer communicate with each other through a plurality of pores to form a movement path of the antifouling fluid,
The porous needle structure layer includes polyethersulfone (PES), polyvinylpyrrolidone (PVP), potassium perchlorate (KClO ₄ ), and dimethylacetamide (DMA),
A method for manufacturing an antifouling member.
A method of removing contaminants using the antifouling member manufactured by the method of manufacturing the antifouling member of claim 6.