KR20210147959A - Antifouling member utilizing surface vibration by vortex and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an antifouling member utilizing surface deformation and a manufacturing method of the antifouling member. According to the present invention, the antifouling member does not include a separate driving unit, and can remove contaminants on the surface of the upper layer by an undulation motion of the middle layer with vibration induced by the vortex formed in an intaglio pattern of the upper layer. By using the dynamic surface by external flow, the antifouling member can continuously generate vibration without including the separate driving unit, thereby capable of effectively blocking the generation and proliferation of microorganisms. The antifouling member includes a base layer, the middle layer, the upper layer, and a needle layer.

Description

Antifouling member utilizing surface vibration by vortex and manufacturing method thereof

The present invention relates to an antifouling member utilizing surface deformation and a method of manufacturing the antifouling member, wherein the antifouling member removes contaminants by changing the surface by vibration without including a separate driving unit by using a dynamic surface by external flow and It relates to a method for manufacturing an antifouling member.

In general, microorganisms including bacteria proliferate after being generated in stagnant water or fluid, and are largely divided into fungi, bacteria, protozoa, algae, etc.

Bacteria multiply and form a protective film when it is unfavorable to self-reproduction, and this protective film is called a biofilm or bacterial biofilm. When bacteria form a biofilm on internal tissues or medical devices of the human body, there is a problem in that the antibacterial effect of antibiotics and chemicals is reduced. In addition, when it is formed on the hull, there is a problem in that the performance of the ship is reduced and the fuel retention amount is increased.

Conventionally, a surface coating method or a chemical grafting method has been mainly used to suppress the generation and proliferation of microorganisms. The surface coating method has a disadvantage in that the coating layer peels off during long-term operation, and the chemical grafting method has a problem in that the reaction conditions are difficult and it is difficult to increase the area. In addition, there is a problem in that microorganisms such as bacteria easily have resistance to chemicals, thereby reducing the antifouling function.

Recently, in order to suppress the generation and proliferation of microorganisms, a method of adding an antifouling paint or an antifouling agent to a fluid, or irradiating a radiation source such as ultraviolet light has been used. However, most of the antifouling paints or antifouling agents contain toxic tri-butyl tin, copper oxide (CuO), and various organic antifouling agents to kill microorganisms, so that the toxic antifouling agent on the surface of the paint gets into water. There is an emission problem. In addition, the method of adding an antifouling paint or an antifouling agent or irradiating a radiation source such as ultraviolet rays has a problem that cannot fundamentally prevent the growth of microorganisms.

In order to solve this problem, in the case of Korean Patent Registration No. 10-1395986, it is possible to more efficiently remove pollutants by adding an excitation means to the bottom of a ship that removes pollutants using a self-polishing type antifouling paint. A device for accelerating the polishing of antifouling paints for ships is provided. However, in Korean Patent Registration No. 10-1395986, since a separate driving unit must be provided to provide vibration to the hull so that the polishing function is not deteriorated, the installation cost increases and the energy supplied to the driving unit is additionally required. have.

Under this background, the present inventors tried to develop an antifouling member capable of fundamentally preventing the generation and proliferation of microorganisms by continuously modifying the surface without using a separate driving unit. As a result, by using a structure designed to form a vortex, even when the external flow is constant, it was discovered that contaminants could be removed with high efficiency by generating surface vibrations, and the present invention was completed.

An object of the present invention is a base layer; an intermediate layer of an elastic material laminated on the base layer; an upper layer laminated on the intermediate layer, in which an embossed pattern and an engraved pattern in which a vortex is formed are repeatedly formed; and a needle layer formed on the embossed pattern in the upper layer, wherein the intermediate layer undulates by vibration induced by the vortex to remove contaminants from the surface of the upper layer.

Another object of the present invention comprising the steps of laminating an intermediate layer of an elastic material on the base layer; laminating an upper layer in which an embossed pattern and an engraved pattern in which a vortex is formed are repeatedly formed on the intermediate layer; and forming a needle layer on the embossed pattern in the upper layer; It is to provide a method of manufacturing an antifouling member comprising a.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those of ordinary skill in the art from the following description.

According to the antifouling member of the present invention, even when the external flow is constant, it is possible to remove contaminants by generating surface vibrations, and it is possible to suppress the generation and proliferation of microorganisms.

According to the antifouling member of the present invention, since a separate driving unit is not included, the configuration is simple and cost can be reduced, and additional power is not required.

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

1 is a view showing the structure of an antifouling member according to an embodiment of the present invention.
2 is a schematic diagram of an antifouling member using a dynamic surface by external flow to remove contaminants according to an embodiment of the present invention.
3 is a view confirming the depth of deformation according to the thickness of the low-hardness elastic material (PDMS, E = 10KPa) by applying an external force to the layer.
Figure 4a shows the pressure distribution when the sinusoidal vibration is applied to the low hardness hydrogel (GelMA and HA) layer.
Figure 4b shows the deformation of the low-hardness hydrogel (GelMA and HA) layer when a sinusoidal vibration is applied to the low-hardness hydrogel (GelMA and HA) layer.
Figure 4c is a view analyzing the deformation when the sinusoidal vibration is applied to the low hardness hydrogel (GelMA and HA) layer.
5a shows the formation of a vortex by the intaglio pattern and the generation of shear stress accordingly.
Figure 5b is a view showing a vortex-induced vibration (vortex-induced vibration).
Figure 6a is a structure that can continuously generate a vortex on the surface of the upper layer even when the external flow is constant.
6b shows a primary flow and a secondary flow.
Fig. 6c shows the vortex formation mechanism on the upper layer surface and in the space of the embossed pattern and the engraved pattern.
7 is a result of confirming the antifouling performance according to the shape of the surface of the upper layer capable of forming various vortices and the shape of the surface of the upper layer.
8 is a view showing the thickness of the needle layer and the height of the needle.
Figure 9a is the result of confirming the culture of E. coli according to the needle interval.
Figure 9b is a graph confirming the antifouling effect by coating the needle with 2-methacryloyloxyethyl phosphorylcholine (MPC).
10A is an example applied to an antifouling member urine catheter manufactured according to an embodiment of the present invention.
10B shows the results of confirming the antifouling effect by applying the antifouling member manufactured according to the embodiment of the present invention to the urine catheter.
11A is an image of an antifouling member having different intermediate layer thicknesses manufactured according to an embodiment of the present invention.
11B is a graph confirming the difference in the area of bacteria formed on the surface of the antifouling member according to the thickness of each intermediate layer manufactured according to the embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes may 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 modifications, equivalents and substitutes for the embodiments are included in the scope of the rights.

The terms used in the examples are used for description purposes only, and should not be construed as limiting the scope of rights. The singular expression includes the plural expression unless the context clearly dictates otherwise. In this specification, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, component, part, or a combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

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

In addition, in the description with reference to the accompanying drawings, the same components are given the same reference numerals regardless of the reference numerals, and the overlapping description 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 thereof will be omitted.

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

1 is a view showing the structure of an antifouling member using a dynamic surface by external flow according to an embodiment of the present invention. 2 is a schematic diagram of an antifouling member using a dynamic surface by external flow to remove contaminants according to an embodiment of the present invention.

1 and 2, the antifouling member using a dynamic surface by external flow according to an embodiment of the present invention, a base layer; an intermediate layer laminated on the base layer; The upper layer is laminated on the intermediate layer, the embossed pattern and the engraved pattern are repeatedly formed; and a needle layer formed on the embossed pattern, and the contaminants on the surface of the upper layer are removed by the vortex formed on the engraved pattern.

In the antifouling member according to an embodiment of the present invention, a vortex may be formed in the intaglio pattern. Vibration is induced by the eddy current formed on the intaglio pattern, and the middle layer moves wavy by the vibration to remove contaminants from the surface of the upper layer.

As used herein, the term “vortex” refers to a flow that swirls in the opposite direction to the mainstream due to the rotational motion of the fluid or the form of a fluid flowing while strongly rotating.

As used herein, the term “undulation” means a wave shape, and “undulation motion” means moving in a wave shape by vibrating up and down.

The base layer may be formed of a flexible and stretchable polymer. When the antifouling member is installed on a ship or offshore facility, it is to be flexibly attached according to the surface shape of the ship or offshore facility. The base layer may be made of at least one of flexible polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), and polyurethane acrylate (PUA), depending on the surface shape. As long as the material can have flexibility, it is not limited thereto.

The intermediate layer is a layer that is laminated on one surface of the base layer and has a constant thickness. The intermediate layer may maintain a constant thickness even if it is deformed by an external force, and at least a portion of the intermediate layer may be deformed into a wave shape by the external force. In order to prevent damage to the structural layer due to a difference in modulus between the intermediate layer and the needle layer, it is formed of an elastic material of low hardness. The elastic material is one or more of polydimethylsiloxane (PDMS), silicone oil, organogel, ecoflex, Triton X, and hydrogel. can be done

In the specification of the present invention, “external force” means a force acting on the intermediate layer by an object other than the intermediate layer, and is not limited thereto as long as it is a force capable of undulating or deforming the intermediate layer or the antifouling material according to the present invention.

Referring to FIG. 3 , it can be seen that the intermediate layer made of the elastic material has a tendency to deform. The deformation depth of the intermediate layer is proportional to the strength of the external force and tends to be inversely proportional to the thickness of the intermediate layer. The thickness of the intermediate layer may be 0.5 mm or more and 2.5 mm or less. Preferably, the depth of deformation of the intermediate layer when the thickness of the intermediate layer is 0.7mm or more so that the needle layer has antifouling performance.

In the specification of the present invention, "deformation depth" means the height of the crest and the valley generated by the wavy motion of the intermediate layer.

Referring to FIGS. 4A, 4B and 4C , the intermediate layer made of the elastic material moves wavy due to vibration.

The upper layer is laminated on one surface of the intermediate layer, and an embossed pattern and an engraved pattern in which a vortex is formed are repeatedly formed. A vortex may be formed in the engraved pattern of the upper layer by the fluid flowing along the surface of the upper layer, and the formed vortex may form a vortex pattern on the surface of the upper layer according to the flow of the fluid. The vortex pattern on the surface of the upper layer induces surface vibration, and the induced vibration acts as an external force on the intermediate layer, so that the intermediate layer may be deformed. The deformed intermediate layer may have a wavy motion to remove contaminants from the surface of the upper layer. Due to the vortex pattern formed on the surface of the upper layer, surface vibration is continuously maintained without a separate driving unit, so that contaminants on the surface of the upper layer can be removed.

As shown in Fig. 5a, the repeated engraving pattern forms a vortex, thereby generating shear stress. The fluid flowing along the surface of the upper layer may have a flow rate of 1 mL/min to 30 mL/min. A flow of fluid within a flow rate of 15 mL/min can form a vortex in the space between the rectangular engraved patterns and form a regular vortex pattern on the surface of the adjacent engraved pattern.

As shown in Figure 5b, the vortex can induce vibrations on the surface.

6A, 6B and 6C , the upper layer surface may have any one of a continuous line type, a discontinuous line type, a sharklet type, and a quasi-sharklet type. can According to the shape of the surface of the upper layer, it is possible to generate a vortex on the surface of the upper layer even when the external flow is constant even without the driving unit. Depending on the shape of the top layer surface, separation of the total flow and recirculation flow between shapes may occur, thereby reducing shear stress near the top layer surface. In particular, the triangular cross section in the shape of a sharklet prevents the flow near the upper layer surface pattern from being disturbed, and widens the spacing between the patterns to enhance the overall flow rate level, and can make the primary flow rate the highest. As shown in the Sharklet structure, flow splitting occurs in the s-shaped pattern unit, and the flow splitting phenomenon generates multiple flows having the same direction. Several flows generated here are called secondary flows. Unlike the simple pattern for generating a non-directional velocity field, a strong secondary flow with a velocity field in the same direction is generated, which has a surface antifouling function. Therefore, the secondary flow between the patterns on the surface of the upper layer can control the antifouling function, and plays a key role. However, the upper surface of the upper layer is not limited thereto as long as it has a shape capable of generating various vortices even without a driving unit.

The width of the embossed pattern on the surface of the upper layer is 2 μm or more. The length of the embossed pattern on the surface of the upper layer is 4 μm to 20 μm in the case of a discontinuous line type, a sharklet type, and a quasi-sharklet type. The height of the embossed pattern on the surface of the upper layer is 2 μm or more.

The embossed pattern on the surface of the upper layer may be a rectangular ridge pattern, and is not limited thereto, as long as it has a shape capable of forming a vortex flow.

The intaglio pattern on the surface of the upper layer may be a hole-shaped pattern, a well-shaped pattern, or a rectangular pattern, but is not limited thereto as long as it has a shape capable of forming a vortex pattern.

The upper layer may be made of polydimethylsiloxane (PDMS) or polyurethane acrylate (PUA).

7 shows the shape of the surface of the upper layer capable of forming various vortices, and is the result of confirming the antifouling performance according to the shape of the surface of the upper layer. Green color indicates microorganisms such as live bacteria, and as a result of performing a microorganism adhesion test such as bacteria, when the surface of the upper layer has a sharklet shape or a quasi-sharklet type compared to other types, microorganism adhesion It can be seen that this is the smallest.

The needle layer is in the form of a thin film laminated on the embossed pattern of the upper layer, and can penetrate and remove contaminants such as bacteria attached to the surface independently of the antifouling function of the middle layer. The shape of the needle layer is not limited as long as it can penetrate bacteria and the like.

8 is a view showing the thickness of the needle layer and the height of the needle. The needle layer is in the form of a thin film, and the thickness of the needle layer may be 10 μm to 200 μm in order to prevent damage to the upper layer due to a difference in modulus with the intermediate layer. When the thickness of the needle layer is less than 10 μm, it is easily damaged by an external force and thus an antifouling effect cannot be obtained, and when the thickness of the needle layer exceeds 200 μm, the formation of a vortex may be hindered. Preferably, the thickness of the needle layer is 100 μm.

The height of the needle may be 100 nm to 500 nm, the lower diameter of the needle may be 100 nm to 300 nm, and the upper diameter of the needle may be 1 nm to 100 nm. A needle pattern having a needle height of less than 100 nm or a nano-needle pattern of several nanometers may rather promote adhesion of microorganisms such as bacteria. Preferably, the height of the needle is 200 nm to 400 nm. When the lower diameter of the needle exceeds 300 nm, it is not possible to have an effect of sterilizing microorganisms such as bacteria. Preferably, the lower diameter of the needle is 200 nm to 300 nm. The upper diameter of the needle is preferably a sharp shape to penetrate microorganisms such as bacteria. Preferably, the upper diameter of the needle is between 1 nm and 10 nm. Preferably, when the lower diameter of the needle is 300 nm, the upper diameter of the needle is less than 10 nm. The sterilization function of such a needle pattern can be derived from the pattern on the surface of the cicada wing.

The antifouling performance of the needle layer is affected by the deformation depth of the intermediate layer, and the thickness of the intermediate layer may be set to have a deformation depth of the intermediate layer for implementing the antifouling performance of the needle layer. Preferably, when the thickness of the intermediate layer is 0.7mm or more, the deformation depth of the intermediate layer can implement the antifouling performance of the needle layer.

Figure 9a is a result of the E. coli culture experiment according to the spacing of the needles, it can be seen that the narrower the spacing between the needles, the better the antifouling performance. Dead bacteria appear in red, while live bacteria appear in green. When the needle spacing is 50 nm, it can be seen that the antifouling performance is improved. The needle spacing is 100 nm to 5 μm. The narrower the needle spacing, the better the antifouling effect. Preferably, the needle spacing is 500 nm.

Figure 9b is a graph confirming the antifouling effect by coating the needle with 2-methacryloyloxyethyl phosphorylcholine (MPC). MPC can improve the antifouling performance of the needle.

According to another embodiment of the present invention, laminating an intermediate layer on the base layer; laminating an upper layer in which an embossed pattern and an intaglio pattern are repeatedly formed on the intermediate layer; And there is provided a method of manufacturing an antifouling member comprising the step of forming a needle layer on the embossed pattern.

The intermediate layer is made of one or more of polydimethylsiloxane (PDMS), silicone oil, organogel, ecoflex, triton X, and hydrogel. A method for manufacturing an antifouling member is provided.

Contaminants on the surface can be removed by using a ship, a sub-water structure, or an artificial organ having a surface coated with an antifouling member manufactured according to an embodiment of the present invention.

The antifouling member manufactured according to the present invention includes an intermittent catheter, a Foley catheter, a tracheal tube, a central venous catheter, and a Swan-liver catheter. Ganz catheter), embryo transfer catheter, umbilical cord catheter (lical line), Tuohy-Borst adapter, intrauterine catheter. In addition, the antifouling member manufactured according to the present invention can be used as an artificial joint, an implant, a ship, an offshore structure, a surface of a water tank used in a display production process, or the inside of a water purification tube.

10A is an example of applying the antifouling member manufactured according to the embodiment of the present invention to a urine catheter. The catheter consists of a supporting layer, a resilient damping layer, an artificial muscle layer, a patterned undulatory wall, and a culture medium from the outside to the inside of the catheter. . The corrugated wall represents a layer having an antifouling member produced according to the present invention.

10B shows the results of confirming the antifouling effect by applying the antifouling member manufactured according to the embodiment of the present invention to the urine catheter. A catheter having a corrugated wall and a catheter having a static wall were stained with crystal violet to compare biofilm formation. It can be seen that the biofilm formation was significantly inhibited in the catheter having a wavy wall.

11A is an image of the intermediate layer thickness of the antifouling member manufactured according to the embodiment of the present invention of 2.1, 1.4, and 0.7 mm, respectively, and the result of the antifouling effect was confirmed by the graph of FIG. 11B . 11B is a graph showing a comparison value of the area of bacteria formed on the surface of the antifouling member manufactured with each different intermediate layer thickness according to an embodiment of the present invention.

<Example. Manufacture of antifouling member utilizing surface vibration caused by vortex>

Nanostructure (NN) or chemical material (zwitter ion such as MPC, 2-methacryloryloxyethyl phosphorylcholine (MPC)) applied layer to prevent surface contamination, and upper layer with PUA or PDMS to generate surface vibration using vortex was formed. In order to cause vortex formation on the surface of the upper layer, the surface of the upper layer was prepared in any one of continuous linear, discontinuous linear, shacklet-like and shacklet-like types, respectively.

As an intermediate layer, among materials with low rigidity to effectively cause turbulence, a material selected from any one of a mixture of PDMS and silicone oil, an organogel, a mixture of PDMS and Ecoplex, and a mixture of PDMS and Trickton X was selected and manufactured.

The thickness of the intermediate layer was prepared as 0.7, 1.4 and 2.1 mm, respectively.

The base layer was made of flexible PET, PDMS or PUA as a cover for surface protection and a layer for attaching to the application surface.

<Experimental Example 1. Antifouling effect according to the surface shape of the upper layer>

The surface of the upper layer was prepared in continuous linear, discontinuous linear, shacklet-like and shacklet-like types, respectively, and as a result of the antifouling effect test, as shown in FIG. It was confirmed that the amount of microbe measurement was remarkably small.

<Experimental Example 2. Antifouling effect according to the thickness of the intermediate layer>

In order to confirm that the depth of deformation of the intermediate layer is proportional to the strength of the external force and has a tendency to be inversely proportional to the thickness of the intermediate layer, the antifouling member was manufactured with the thickness of the intermediate layer of 0.7, 1.4 and 2.1 mm, respectively, as shown in FIG. 11a below.

As a result, when referring to the graph of FIG. 11B below, it was confirmed that the antifouling effect decreased as the thickness of the intermediate layer was reduced to 2.1, 1.4, and 0.7 mm as indicated in red. In this case, the value of the graph y-axis means the area where bacteria are formed, and the greater the difference compared to the untreated surface, the greater the antifouling effect.

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

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

Claims (11)

base layer;
an intermediate layer laminated on the base layer;
An upper layer laminated on the intermediate layer, in which an embossed pattern and an engraved pattern are repeatedly formed; And
a needle layer formed on the embossed pattern;
including,
Contaminants on the surface of the upper layer are removed by a vortex formed on the intaglio pattern, an antifouling member.
According to claim 1,
The deformation depth of the intermediate layer is proportional to the strength of the external force, and inversely proportional to the thickness of the intermediate layer, antifouling member.
3. The method of claim 1 or 2,
The thickness of the intermediate layer is 0.5 mm or more and 2.5 mm or less, the antifouling member.
3. The method of claim 1 or 2,
The antifouling member, wherein the upper layer surface has any one of a continuous line type, a discontinuous line type, a sharklet type and a quasi-sharklet type.
3. The method of claim 1 or 2,
The thickness of the needle layer is 10 μm to 200 μm, the antifouling member.
3. The method of claim 1 or 2,
The height of the needle formed in the needle layer is 100 nm to 500 nm, the lower diameter of the needle is 100 nm to 300 nm, and the upper diameter of the needle is 1 nm to 100 nm, the antifouling member.
3. The method of claim 1 or 2,
The base layer is made of at least one of flexible polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), and polyurethane acrylate (PUA).
3. The method of claim 1 or 2,
The intermediate layer is made of at least one of polydimethylsiloxane (PDMS), silicone oil, organogel, ecoflex, Triton X, and hydrogel. , the absence of antifouling.
3. The method of claim 1 or 2,
The upper layer is made of polyurethane acrylate (Poly urethane acrylate, PUA) or polydimethylsiloxane (PDMS), antifouling member.
laminating an intermediate layer on the base layer;
laminating an upper layer in which an embossed pattern and an intaglio pattern are repeatedly formed on the intermediate layer; and
forming a needle layer on the embossed pattern;
A method for manufacturing the antifouling member of claim 1, comprising a.
11. The method of claim 10,
The intermediate layer is made of one or more of polydimethylsiloxane (PDMS), silicone oil, organogel, ecoflex, triton X, and hydrogel. A method for manufacturing an antifouling member.

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