Method for synthesizing Anti-biofouling polymer thin film having chemical durability and Anti-corrosion properties

Abstract

An embodiment of the present invention can provide an anti-biofouling polymer thin film having chemical stability and excellent performance. This thin film can exhibit excellent anti-biofouling performance in various in vivo environments through excellent anti-biofouling performance even in various pH environments, and can be used in medical devices and biomaterials that require both anti-biofouling and anti-corrosion properties.

Description

Method for synthesizing anti-biofouling polymer thin films with chemical durability and corrosion-resistant properties

[0001] The present invention relates to a method for synthesizing an anti-biofouling polymer thin film having chemical durability and corrosion-resistant properties.

[0002] Anti-biofouling coatings are a key technology that prevents nonspecific adhesion of various biomolecules, including proteins, cells, and metabolites, to the surfaces of medical devices and biomaterials (implants, ingestibles, wearable devices, etc.).

[0003] Nonspecific adsorption of proteins or cells onto the surface of biomaterials can trigger an immune response or lead to functional impairment. Furthermore, bacterial infection can lead to the formation of biofilms, posing a threat to patient health.

[0004] To solve these problems, anti-biofouling coating technology has been developed, and in particular, coating technology using hydrophilic polymer thin films has been developed.

[0005] Representative examples include hydrophilic polymer films, such as poly(ethylene glycol) (PEG) and 2-hydroxyethyl methacrylate (HEMA). The anti-biofouling principle of hydrophilic polymer films is known to be the formation of a hydration layer on the surface, forming a physical and energetic barrier against nonspecific adsorption of external substances.

[0006] However, the low chemical and oxidative stability of PEG, HEMA, and other materials in the body has recently become a problem. To address this, zwitterionic polymers (polyampholytes) are being actively developed. These are recognized as a promising antifouling coating technology due to their superior performance, oxidative stability, and biocompatibility compared to existing anti-biofouling polymers.

[0007] Corrosion-resistant coatings are a technology that can ensure patient safety by reducing the risk of metal ion release due to corrosion during long-term use of medical devices and biomaterials. Recently, technologies have been developed that incorporate superhydrophobic polymers and cross-linked polymer layers that inhibit the penetration of corrosive ions. However, their corrosion-resistant properties still have limitations. To achieve more effective corrosion-resistant properties, a coating that exhibits excellent chemical stability in the body environment and resists swelling and peeling in solution environments is essential.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] (Patent Document 0001) KR 10-2020-0128514 A

[0011] The technical problem to be achieved by the present invention is to provide a method for synthesizing a polymer thin film that has anti-biofouling properties in various pH ranges and exhibits excellent chemical durability for a long period of time even in a very low pH environment.

[0012] The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0013] In order to achieve the above technical task, one embodiment of the present invention provides a method for synthesizing an anti-biofouling polymer thin film, comprising: a step of forming a polymer layer on a substrate in a chamber through an iCVD process; and a step of crosslinking the formed polymer layer through a UV post-treatment; wherein the polymer layer includes poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) and (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide), and is characterized in that the component changes from poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) to (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) as the component moves away from the substrate.

[0014] In an embodiment of the present invention, the step of forming the polymer layer may be characterized in that the coating is performed by flowing the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) into the chamber, and then the amount of the flowing poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) is reduced while flowing the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide).

[0015] In an embodiment of the present invention, it may be characterized in that only the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) is positioned at the lowest layer of the polymer layer, only the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) is positioned at the highest layer, and the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) and the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) are mixed and present in the intervening portion.

[0016] In an embodiment of the present invention, the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) may be characterized in that it is manufactured through mixing 2-carboxyethyl acrylate and N-[3-(Dimethylamino)propyl]acrylamide.

[0017] In an embodiment of the present invention, it may be characterized in that the ratio of the 2-carboxyethyl acrylate and the N-[3-(Dimethylamino)propyl]acrylamide is 1:1.

[0018] In order to achieve the above technical task, another embodiment of the present invention provides an anti-biofouling polymer thin film formed by including poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) and (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide).

[0019] In an embodiment of the present invention, it may be characterized in that only the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) is positioned at the lowest layer of the polymer layer of the thin film, only the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) is positioned at the highest layer, and the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) and the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) are mixed and present in the intervening portion.

[0020] In an embodiment of the present invention, the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) may be characterized by including 2-carboxyethyl acrylate and N-[3-(Dimethylamino)propyl]acrylamide.

[0021] In an embodiment of the present invention, it may be characterized in that the ratio of the 2-carboxyethyl acrylate and the N-[3-(Dimethylamino)propyl]acrylamide is 1:1.

[0022] In an embodiment of the present invention, it can be characterized by being synthesized by the above synthesis method.

[0023] According to an embodiment of the present invention, an anti-biofouling polymer thin film having chemical stability and excellent performance can be provided.

[0024] It can exhibit excellent anti-biofouling performance in various body environments through excellent anti-biofouling performance even in various pH environments, and can be utilized as a medical device and biomaterial that requires both anti-biofouling and corrosion prevention properties.

[0025] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the composition of the invention described in the claims.

[0026] Figure 1a is an image illustrating a method for synthesizing an anti-biofouling polymer thin film, and Figure 1b is an image illustrating the chemical structure of the anti-biofouling polymer thin film.

[0027] Figure 2a is a graph showing the swelling phenomenon and refractive index change analysis of an anti-biofouling polymer in a water environment, and Figure 2b is an image schematically showing the thin film formation and the anti-fouling phenomenon of an anti-biofouling polymer thin film.

[0028] Figure 3a is a graph showing the zeta-potential change of a pCDm polymer thin film according to the control of CaEA and DMAPAAm fractions and the elemental fraction change through XPS analysis, Figure 3b is a graph showing the optimization of the anti-biofouling properties of a pCDm polymer thin film for proteins according to the control of the fractions, and Figure 3c is a graph showing the fraction control aspect of a pCDm polymer thin film through FT-IR analysis.

[0029] Figure 4a is a graph showing the gradual change in monomer composition in the vertical direction of a pCDm-grad-pV4D4 polymer thin film through XPS depth profiling analysis, and Figure 4b is a graph showing the water contact angle analysis of a pV4D4 thin film and a pCDm-grad-pV4D4 thin film on various substrates.

[0030] Figure 5a is a roughness analysis image of a pCDm-grad-pV4D4 thin film through AFM analysis, and Figure 5b is a transparency analysis graph in the visible light region of a 500 nm pCDm-grad-pV4D4 thin film.

[0031] Fig. 6a is an image illustrating the corrosion prevention mechanism of the pCDm-grad-pV4D4 polymer layer, Fig. 6b is a graph confirming the corrosion prevention characteristics of pCDm-grad-pV4D4 through a Tafel plot, and Fig. 6c is a graph confirming the corrosion prevention characteristics of pCDm-grad-pV4D4 through a Nyquist plot.

[0032] Figure 7 is an image showing the corrosion pattern of Cu over time in a pH 1.00 PBS solution with or without a 500 nm pCDm-grad-pV4D4 coating using SEM surface measurement.

[0033] Figure 8a is an image confirming the anti-biofouling performance for FITC-BSA (a protein with a fluorescent material attached), Figure 8b is an image confirming the anti-biofouling performance for NIH 3T3 fibroblasts (cells), and Figure 8c is a graph confirming the anti-biofouling performance for cells.

[0034] Figure 9 is a graph comparing the anti-biofouling performance of PEG and pCDm-grad-pV4D4 thin films through protein adsorption experiments.

[0035] Figure 10 is a graph showing the anti-biofouling performance of a pCDm-grad-pV4D4 polymer thin film after 24 h of exposure to various solvent conditions.

[0036] Figure 11 shows pCDm-grad-pV4D4 after exposure to pH 1.00 PBS solution at different time points.

[0037] This is a graph confirming the anti-biofouling performance of the thin film.

[0038] Figure 12 is a graph confirming the anti-biofouling performance of a pCDm-grad-pV4D4 thin film under various pH conditions.

[0039] Hereinafter, the present invention will be described with reference to the attached drawings. However, the present invention can be implemented in various different forms and is therefore not limited to the embodiments described herein. In the drawings, irrelevant parts have been omitted for clarity of description, and similar parts have been designated with similar reference numerals throughout the specification.

[0040] Throughout the specification, when a part is said to be "connected (connected, contacted, or coupled)" to another part, this includes not only cases where it is "directly connected," but also cases where it is "indirectly connected" with another part in between. Furthermore, when a part is said to "include" a component, this does not exclude other components, but rather implies that it may include other components, unless otherwise specifically stated.

[0041] The terminology used herein is merely used to describe 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 this specification, it should be understood that the terms "comprises" or "has" indicate the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0042] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

[0043]

[0044] The terms used in this specification are defined as follows.

[0045] “pV4D4” stands for poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane), a polymer layer.

[0046] “pCDm” stands for poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide), an amphoteric polyelectrolyte with a hydrophilic polymer layer.

[0047] “pCDm-grad-pV4D4” refers to a polymer thin film synthesized according to the present invention.

[0048] pCDm-grad-pV4D4, pCDm-grad-pV4D4 polymer thin film, pCDm-grad-pV4D4 thin film all mean the same thing.

[0049] “CaEA” stands for 2-carboxyethyl acrylate.

[0050] “DMAPAAm” stands for N-[3-(Dimethylamino)propyl]acrylamide.

[0051]

[0052] Figure 1a is an image illustrating a method for synthesizing an anti-biofouling polymer thin film, and Figure 1b is an image illustrating the chemical structure of the anti-biofouling polymer thin film.

[0053] Referring to FIGS. 1A and 1B, a method for synthesizing an anti-biofouling polymer thin film according to an embodiment of the present invention is described.

[0054] When proteins and bacteria are absorbed onto the surface of medical materials or devices inserted into the human body and home appliance materials, causing contamination (biofouling), the risk of developing diseases such as bacterial sepsis, pneumonia, and food poisoning increases, making the development of preventive technologies crucial.

[0055] Conventionally, the synthesis of polymers exhibiting anti-biofouling and corrosion-resistant properties has required a highly complex process. Furthermore, most anti-biofouling coatings are manufactured using solution processes, potentially leading to toxicity issues due to unremoved solvents. Therefore, the present invention provides a method for forming a polymer film with superior anti-biofouling and corrosion-resistant properties and superior chemical durability through a simple process.

[0056] In order to solve these problems, an anti-biofouling polymer thin film synthesis method according to one embodiment of the present invention includes a step of forming a polymer layer on a substrate in a chamber through an iCVD (initiated chemical vapor deposition) process; and a step of crosslinking the formed polymer layer through UV post-treatment.

[0057] The above polymer layer comprises pV4D4 and pCDm.

[0058] Additionally, the constituents of the polymer layer may change from pV4D4 to pCDm as they move away from the substrate.

[0059] pV4D4 may be a polymer layer that enhances adhesion to a substrate while imparting corrosion-prevention properties. Thus, pV4D4 may be coated on a substrate by flowing it into a chamber.

[0060] That is, the step of forming a polymer layer can be performed by flowing the pV4D4 into the chamber to perform coating, and then reducing the amount of the pV4D4 that is flowed while flowing the pCDm. Accordingly, only the pV4D4 can be positioned at the lowest part of the polymer layer, only the pCDm can be positioned at the highest part, and the pV4D4 and the pCDm can be mixed and present in the area between them.

[0061] pCDm can be a hydrophilic polymer layer that imparts excellent anti-biofouling properties as an amphoteric polymer electrolyte.

[0062] The above pCDm can be prepared by mixing CaEA and DMAPAAm.

[0063] CaEA and DMAPAAm exhibit anionic (acidic) and cation (basic) properties, respectively. Specifically, anti-biofouling performance is maximized when the ratio of the two substances responsible for anion and cation is symmetrical (1:1), resulting in a neutral state where the surface charge converges to '0'.

[0064] Accordingly, the fraction of CaEA and DMAPAAm can be optimized for manufacturing at a point where the ratio of the two substances becomes 1:1. This fraction can be controlled by controlling the flow rate.

[0065] The UV post-treatment crosslinking process may be a post-treatment process using 302 nm UV.

[0066]

[0067] Hereinafter, an anti-biofouling polymer thin film according to another embodiment of the present invention is described.

[0068] An anti-biofouling polymer thin film according to one embodiment of the present invention can be formed by including pV4D4 and pCDm.

[0069] As the component of the polymer layer moves away from the substrate, it can change from pV4D4 to pCDm.

[0070] pV4D4 can be a polymer layer that enhances adhesion to the substrate while imparting corrosion-prevention properties. Thus, pV4DV can be coated on the substrate by flowing it into the chamber.

[0071] Accordingly, only the pV4D4 may be present at the lowest layer of the polymer layer of the thin film, only the pCDm may be present at the highest layer, and the pV4D4 and the pCDm may be present in a mixed form in the middle portion.

[0072] pCDm can be a hydrophilic polymer layer that imparts excellent anti-biofouling properties as an amphoteric polymer electrolyte.

[0073] The above pCDm can be prepared by mixing CaEA and DMAPAAm.

[0074] CaEA and DMAPAAm exhibit anionic (acidic) and cation (basic) properties, respectively. Specifically, anti-biofouling performance is maximized when the ratio of the two substances responsible for anion and cation is symmetrical (1:1), resulting in a neutral state where the surface charge converges to '0'.

[0075] Accordingly, the fraction of CaEA and DMAPAAm can be optimized for manufacturing at a point where the ratio of the two substances becomes 1:1. This fraction can be controlled by controlling the flow rate.

[0076] An anti-biofouling polymer thin film can be synthesized by the above synthesis method.

[0077]

[0078] Hereinafter, embodiments and experimental examples of the present invention will be described in detail.

[0079]

[0080] <Example>

[0081] Example 1: Preparation of CaEA and DMAPAAm copolymer thin film with maximized anti-biofouling performance

[0082] After preparing substrates such as Si wafer, slide glass, polystyrene series 96 well plate, TCPS, etc., a copolymer of CaEA and DMAPAAm is synthesized using the iCVD process to form a thin film layer.

[0083] To this end, CaEA, DMAPAAm, and the initiator tert-butyl peroxide (TBPO) are each vaporized and injected into the iCVD process chamber, and then a pCDm polymer thin film layer is manufactured through free radical polymerization.

[0084] To initiate free radical polymerization, the filament inside the chamber was maintained at 160°C, and the substrate temperature was maintained at 37°C. During the reaction, the process pressure of the iCVD process chamber was fixed at 100 mTorr.

[0085] In this process, the flow ratio of monomer and initiator was maintained at a ratio of CaEA: DMAPAAm: TBPO=1:1:0.05.

[0086] The pCDm layer was finally fabricated by performing a post-treatment with 302 nm UV for 10 minutes on the polymerized and thin-film coated pCDm layer through the iCVD process.

[0087]

[0088] Example 2: Preparation of an anti-biofouling and anti-corrosion polymer film exhibiting gradual component changes in the direction of coating.

[0089] As in Example 1, substrates such as Si wafer, slide glass, polystryene series 96 well plate, TCPS, etc. are prepared and then placed in the iCVD process chamber.

[0090] Then, after the chamber is made into a vacuum state of approximately 40 mTorr, V4D4 and TBPO are vaporized and injected into the iCVD process chamber, and a pV4D4 polymer thin film layer is formed through free radical polymerization.

[0091] To initiate free radical polymerization, the filament inside the chamber was maintained at 160°C, and the substrate temperature was also fixed at 37°C, as in Example 1. During the reaction, the process pressure of the iCVD process chamber was fixed at 100 mTorr.

[0092] In this process, each flow rate was maintained at a ratio of V4D4:TBPO=1:0.05.

[0093] After forming a pV4D4 thin film of approximately 200 nm on a Si wafer, CaEA and DMAPAAm were maintained at a flow ratio of V4D4:CaEA:DMAPAAm=1:1:1:0.05 during the iCVD process.

[0094] The iCVD process was performed by gradually lowering the flow rate of V4D4, and finally a thin film layer was formed so that only a pCDm layer without V4D4 existed at the top layer.

[0095] Through this, a pCDm-grad-pV4D4 polymer thin film layer was produced. As in Example 1, this was post-treated with 302 nm UV for 10 minutes to complete the final pCDm-grad-pV4D4 polymer thin film layer.

[0096]

[0097] <Comparative Example>

[0098] Comparative Example 1: Preparation of mPEG thin film

[0099] A Si wafer, 96 well plate was prepared as a substrate, and hydroxyl groups were formed on the surface using plasma equipment.

[0100] To this end, after each substrate was injected into the plasma equipment, the plasma equipment was placed in a vacuum state of 10 mTorr.

[0101] Afterwards, 20 sccm of oxygen was injected and 50 W of plasma was applied for 1 minute to introduce hydrophilic hydroxyl groups to the surface of each substrate.

[0102] And, the mPEG thin film layer was produced by immersing it in a 0.1% mPEG (solvent: methanol) solution for 24 hours.

[0103]

[0104] <Experimental Example>

[0105] Experimental Example 1: Measurement of swelling ratio and refractive index of polymer thin films (Fig. 2a and Fig. 2b)

[0106] Figure 2a is a graph showing the swelling phenomenon and refractive index change analysis of an anti-biofouling polymer in a water environment, and Figure 2b is an image schematically showing the thin film formation and the anti-fouling phenomenon of an anti-biofouling polymer thin film.

[0107] Referring to FIGS. 2a and 2b, the anti-biofouling polymer film according to an embodiment of the present invention swells very highly, about 200%, in a water environment, forms a hydration layer on the surface, and exhibits anti-biofouling properties against proteins or cells (FIG. 2a). In addition, it forms a physical and energy barrier against non-specific adsorption on the surface, similar to the anti-biofouling mechanism of existing hydrophilic polymers (FIG. 2b).

[0108]

[0109] Experimental Example 2: Analysis of FT-IR, zeta-potential, and protein adhesion amount according to monomer ratio of polymer thin films (Figs. 3a to 3c)

[0110] Figure 3a is a graph showing the zeta-potential change of a pCDm polymer thin film according to the control of CaEA and DMAPAAm fractions and the elemental fraction change through XPS analysis, Figure 3b is a graph showing the optimization of the anti-biofouling properties of a pCDm polymer thin film for proteins according to the control of the fractions, and Figure 3c is a graph showing the fraction control aspect of a pCDm polymer thin film through FT-IR analysis.

[0111] Referring to FIGS. 3a to 3c, the pCDm layer, which is a polyampholyte invented in the present invention, was developed by optimizing the ratio of the two substances to 1:1 by adjusting the fraction of CaEA and DMAPAAm. CaEA and DMAPAAm each exhibit the characteristics of anion (acidity) and cation (base), respectively. In particular, when designing a polyampholyte material, the anti-biofouling performance is the highest when the ratio of the two substances responsible for the anion and cation is symmetrical at 1:1 so that the surface charge converges to '0' and becomes neutral. This can be done by adjusting the fraction of CaEA and DMAPAAm by adjusting the flow rate, and the point where the two substances are contained in a 1:1 ratio was found by checking the zeta-potential and elemental composition ratio according to the fraction (FIG. 3a). Through an antifouling performance test for proteins, it was confirmed that the anti-biofouling performance is the best at the optimized point (FIG. 3b). Additionally, it can be confirmed through FT-IR analysis that the fraction control is well achieved (Fig. 3c).

[0112]

[0113] Experimental Example 3: Physical property analysis of pCDm-grad-pV4D4 thin film: XPS depth profile, water contact angle (Figs. 4a to 5b)

[0114] Figure 4a is a graph showing the gradual change in monomer composition in the vertical direction of a pCDm-grad-pV4D4 polymer thin film through XPS depth profiling analysis, and Figure 4b is a graph showing the water contact angle analysis of a pV4D4 thin film and a pCDm-grad-pV4D4 thin film on various substrates.

[0115] Referring to FIGS. 4a and 4b, the formation of a pCDm-grad-pV4D4 layer can be confirmed through XPS depth profiling analysis (FIG. 4a). In addition, it can be confirmed through water contact angle analysis that the pCDm-grad-pV4D4 layer coated through the iCVD process can impart excellent hydrophilicity regardless of the type of substrate (FIG. 4b).

[0116]

[0117] Figure 5a is a roughness analysis image of a pCDm-grad-pV4D4 thin film through AFM analysis, and Figure 5b is a transparency analysis graph in the visible light region of a 500 nm pCDm-grad-pV4D4 thin film.

[0118] Referring to Figures 5a and 5b, the excellent flatness of the pCDm-grad-pV4D4 thin film can be confirmed through AFM analysis (Figure 5a). In addition, the excellent transparency of the thin film coated to approximately 500 nm in the visible light range can also be confirmed (Figure 5b).

[0119]

[0120] Experimental Example 4: Examination of the corrosion-prevention properties of pCDm-grad-pV4D4 thin films (Figs. 6a to 7)

[0121] Fig. 6a is an image illustrating the corrosion prevention mechanism of the pCDm-grad-pV4D4 polymer layer, Fig. 6b is a graph confirming the corrosion prevention characteristics of pCDm-grad-pV4D4 through a Tafel plot, and Fig. 6c is a graph confirming the corrosion prevention characteristics of pCDm-grad-pV4D4 through a Nyquist plot.

[0122] Referring to Figures 6a to 6c, the anti-biofouling polymer thin film is not limited to simple antifouling properties, but can also easily impart corrosion-prevention performance (bio-passivation) without the complexity of the process through the iCVD process (Figure 6a). In addition, the corrosion-prevention properties can be confirmed through electrochemical analysis, such as the Tafel plot in Figure 6b and the Nyquist plot in Figure 6c, and it can be confirmed that both the corrosion tendency and the corrosion rate are reduced (Figures 6b and 6c).

[0123]

[0124] Figure 7 is an image showing the corrosion pattern of Cu over time in a pH 1.00 PBS solution with or without a 500 nm pCDm-grad-pV4D4 coating using SEM surface measurement.

[0125] Referring to Fig. 7, a 500 nm pCDm-grad-V4D4 polymer thin film was coated on copper (Cu) and the corrosion phenomenon was confirmed according to the exposure time in a pH 1.00 PBS solution environment, and it was confirmed that it has excellent corrosion prevention properties.

[0126]

[0127] Experimental Example 5: Examination of protein adhesion prevention performance of pCDm-grad-pV4D4 thin film (Figs. 8a to 12)

[0128] Figure 8a is an image confirming the anti-biofouling performance for FITC-BSA (a protein with a fluorescent material attached), Figure 8b is an image confirming the anti-biofouling performance for NIH 3T3 fibroblasts (cells), and Figure 8c is a graph confirming the anti-biofouling performance for cells.

[0129] Referring to FIGS. 8a to 8c, it can be confirmed that the pCDm-grad-pV4D4 thin film exhibits excellent anti-biofouling performance without adsorption or contamination.

[0130]

[0131] Figure 9 is a graph comparing the anti-biofouling performance of PEG and pCDm-grad-pV4D4 thin films through protein adsorption experiments.

[0132] Referring to Fig. 9, it can be confirmed that the pCDm-grad-pV4D4 thin film exhibits excellent anti-biofouling performance with almost no protein adsorption.

[0133]

[0134] Figure 10 is a graph showing the anti-biofouling performance of a pCDm-grad-pV4D4 polymer thin film after 24 h of exposure to various solvent conditions.

[0135] Referring to Fig. 10, it can be confirmed that the pCDm-grad-pV4D4 polymer thin film has excellent anti-biofouling performance without protein adsorption even under various solvent conditions.

[0136]

[0137] Figure 11 is a graph showing the anti-biofouling performance of a pCDm-grad-pV4D4 thin film after exposure to a pH 1.00 PBS solution at different time points.

[0138] Referring to Fig. 11, it can be confirmed that the pCDm-grad-pV4D4 thin film has excellent anti-biofouling performance even under strong acid conditions for two weeks.

[0139]

[0140] Figure 12 is a graph confirming the anti-biofouling performance of a pCDm-grad-pV4D4 thin film under various pH conditions.

[0141] Referring to Fig. 12, it can be confirmed that the pCDm-grad-pV4D4 thin film has excellent anti-biofouling performance even under various pH conditions.

[0142]

[0143] The pCDm-grad-pV4D4 thin film according to the present invention was confirmed to have chemical stability and excellent anti-biofouling performance. The excellent chemical stability achieved can be said to have solved a problem that existing anti-biofouling hydrophilic polymers, such as PEG and zwitterionic polymers, have not been able to easily solve. Furthermore, the excellent anti-biofouling performance demonstrated even in various pH environments is expected to demonstrate excellent anti-biofouling performance in complex and diverse in vivo environments, and has high utility as a solution that opens up the possibility of long-term use of medical devices and biomaterials.

[0144] This polymer film, manufactured using the iCVD vapor deposition process, can be applied to any substrate, and as a solvent-free coating with excellent biocompatibility, it will have a positive impact on the medical device industry. Furthermore, because it imparts corrosion-resistant properties without requiring additional processing, it offers significant benefits from an engineering perspective, enhancing the practical applicability of the polymer film developed in this invention.

[0145]

[0146] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0147] The scope of the present invention is indicated by the claims described below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. A step of forming a polymer layer on a substrate inside a chamber through an iCVD process; and A crosslinking step of the formed polymer layer through UV post-treatment; A method for synthesizing an anti-biofouling polymer thin film, characterized in that the polymer layer comprises poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) and (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide), and the component changes from poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) to (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) as the component moves away from the substrate.

2. In paragraph 1, The step of forming the polymer layer is: A method for synthesizing an anti-biofouling polymer thin film, characterized in that the coating is performed by flowing the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) into the chamber, and then the amount of the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) flowing is reduced.

3. In paragraph 1, An anti-biofouling polymer thin film synthesis method, characterized in that only the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) is located at the lowest layer of the polymer layer, only the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) is located at the top layer, and the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) and the (polyampholyte) poly(2-carboxyethylacrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) are mixed and present in the intervening portion.

4. In paragraph 1, An anti-biofouling polymer thin film synthesis method, characterized in that the above (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) is produced by mixing 2-carboxyethyl acrylate and N-[3-(Dimethylamino)propyl]acrylamide.

5. In paragraph 4, Anti-, characterized in that the ratio of the above 2-carboxyethyl acrylate and the above N-[3-(Dimethylamino)propyl]acrylamide is 1:

1. -Method for synthesizing biofouling polymer thin films. 6.Anti-biofouling polymer thin film formed by including poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) and (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide).

7. In paragraph 6, An anti-biofouling polymer thin film, characterized in that only the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) is located at the lowest layer of the polymer layer of the thin film, only the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) is located at the top layer, and the poly(2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane) and the (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) are mixed and present in the intervening region.

8. In paragraph 6, The above (polyampholyte) poly(2-carboxyethyl acrylate-co-N-[3-(Dimethylamino)propyl]acrylamide) is an anti-biofouling polymer thin film characterized by containing 2-carboxyethyl acrylate and N-[3-(Dimethylamino)propyl]acrylamide.

9. In paragraph 8, An anti-biofouling polymer thin film, characterized in that the ratio of the 2-carboxyethyl acrylate and the N-[3-(Dimethylamino)propyl]acrylamide is 1:

1.

10. In paragraph 6, An anti-biofouling polymer thin film characterized by being synthesized by the synthetic method of claim 1.

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