New-type antifouling developing coating material, and preparation method therefor and use thereof

Abstract

A new-type antifouling developing coating material, and a preparation method therefor and the use thereof. The antifouling developing coating material has a structure represented by formula I. Compared with a traditional developing coating, the antifouling developing coating material has higher medical safety, can ensure the stability and durability of a developing effect, and has a wider range of application.

Description

A new antifouling developing coating material and its preparation method and application Technical Field

[0001] The present application relates to the field of medical material technology, for example, a new anti-fouling developing coating material and its preparation method and application. Background Art

[0002] Medical developer coatings play a key role in medical imaging. Advances in medical imaging are driving higher demands on their safety and effectiveness. Medical developer coatings must exhibit excellent antifouling properties, effectively resisting bacterial protein adhesion to prevent bacterial infection and cross-infection, while maintaining a clean and transparent surface to ensure clear and accurate images. Furthermore, medical developer coatings must provide clear and accurate development capabilities.

[0003] 1. Importance and research progress of antifouling performance:

[0004] Medical antifouling developer coatings originated from improvements to traditional developer coatings. While traditional developer coatings provide development capabilities, their antifouling properties are limited. With the increasing use of medical devices, the demand for these coatings has become more pressing. Therefore, scientists have begun researching ways to improve antifouling performance by incorporating antifouling materials. The antifouling principle primarily involves the hydrophilicity and lipophilicity of the material surface. Hydrophilic surfaces create a high contact angle with water, preventing moisture and impurities from settling. Lipophilic surfaces prevent the adhesion of organic matter and oils, reducing the adsorption of biomolecules.

[0005] In recent years, research on medical antifouling coatings has made significant progress. Researchers have manipulated surface properties to develop superior antifouling coatings. For example, the introduction of super-hydrophobic polymers creates a super-hydrophobic surface, enabling efficient self-cleaning and antifouling properties. Furthermore, biomimetic design of specialized surface structures, such as micro-nano-concave and convex shapes and honeycomb patterns, reduces surface contact area and reduces the adhesion of pollutants. Bioactive molecules are embedded in the coating to form a "sterilization zone," inhibiting microbial growth and enhancing antifouling effectiveness.

[0006] 2. Importance and research progress of developing performance:

[0007] The development performance of medical anti-fouling developer coatings critically impacts medical image clarity and diagnostic accuracy. Developer coatings must be sensitive to X-rays to ensure effective development under X-ray irradiation. Development technology is widely used in medical imaging, creating a clear image by developing image-sensitive materials. X-ray development is a common technique that relies on the absorption and scattering of X-rays. Developer coatings play a key role in this process, absorbing and scattering X-rays to produce images.

[0008] Research on medical developer coatings continues to advance alongside advances in medical imaging technology. Researchers are refining developer and coating chemistry to improve development efficiency and image quality. Simultaneously, the introduction of new technologies such as nanotechnology and quantum dots is enhancing coating sensitivity and selectivity.

[0009] 3. Challenges and research directions of combining development and antifouling:

[0010] Combining developer and antifouling functions remains a challenge, requiring both developer performance and excellent antifouling properties. However, the interaction between developers and antifouling agents can reduce developer efficiency. Coating material selection and structural design require greater care to achieve an optimal balance between developer and antifouling performance. To address this challenge, researchers can explore diverse combinations of developers and antifouling agents and optimize coating structure and chemical composition. Furthermore, nanotechnology and surface engineering are being used to construct multifunctional developer coatings, synergistically enhancing developer and antifouling performance.

[0011] Overall, medical developer coatings are crucial in medical imaging. By continuously improving developer performance and antifouling capabilities, we can develop more advanced, safer, and more reliable developer coatings, providing better technical support for medical diagnosis and treatment. Furthermore, research combining developer and antifouling capabilities is expected to bring new breakthroughs to the development of medical developer materials.

[0012] Application Contents

[0013] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0014] The present application provides a novel antifouling developing coating material and its preparation method and application, so as to develop a developing coating with better performance, greater safety and reliability, and provide better technical support for medical diagnosis and treatment.

[0015] In one aspect, the present application provides a novel anti-fouling and developing coating material, wherein the novel anti-fouling and developing coating material has a structure as described in Formula I below:

[0016] wherein m=1-40 (e.g., 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40, etc.), n=1-40 (e.g., 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40, etc.), and k=1-3 (e.g., 1, 2, or 3).

[0017] The anti-fouling and developing coating material described in this application combines anti-fouling and developing through covalent bonding technology, thereby ensuring the stability of the material and the stability of the anti-fouling and developing properties, so that the material has outstanding performance in both anti-fouling performance and developing effect, making it have broad application prospects in the field of medical imaging, and providing strong support for the safety of medical equipment and the accuracy of medical images.

[0018] In some optional embodiments, the imaging agent is one selected from iohexol, iohexol hydrolyzate, iopromide, meglumine diatrizoate, sodium diatrizoate, iodized oil and iodixanol, or a mixture of at least two thereof.

[0019] In a further alternative embodiment, the imaging agent is iohexol or iohexol hydrolyzate.

[0020] In some optional embodiments, the developer is connected to the siloxane via a linking group.

[0021] In some optional embodiments, the developer is connected to the siloxane by forming a Si-O-Si linkage.

[0022] In some optional embodiments, the anti-fouling developing coating material has a structure shown in the following formula II:

[0023] wherein m=1-40 (e.g., 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40), n=1-40 (e.g., 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40), k=1-3 (e.g., 1, 2, or 3), R is selected from a C1-C5 alkyl group or a C1-C5 alkylsilyl group, and L is

[0024] In some optional embodiments, m:n = 1:1 to 4:1, for example, 1:1, 2:1, 3:1, or 4:1. In the present application, the ratio of m:n is within 1:1 to 4:1. By adjusting the molar ratio of the modified phosphorylcholine polymer to the barium salt, the polymer material that meets the requirements of development and antifouling can be obtained.

[0025] In some alternative embodiments, m:n=3:1.

[0026] On the other hand, the present application provides a method for preparing the novel anti-fouling developing coating material as described above, the preparation method comprising the following steps:

[0027] The developer modified by the siloxane reagent is subjected to a hydrolysis and polycondensation reaction with the modified phosphorylcholine polymer modified by the siloxane to obtain the novel anti-fouling developing coating material.

[0028] Optionally, the siloxane agent is selected from

[0029] Optionally, the molar ratio of the siloxane reagent modified developer to the siloxane modified phosphorylcholine polymer is 40:1 to 10:1, for example, 40:1, 38:1, 35:1, 33:1, 30:1, 28:1, 25:1, 20:1, 18:1, 15:1, 13:1, 10:1, etc.

[0030] Optionally, the hydrolysis and condensation reaction of the siloxane reagent-modified developer and the siloxane-modified modified phosphorylcholine polymer is carried out at room temperature, and the reaction time is 12 to 48 hours, for example, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 24 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours or 48 hours, and can be 24 hours.

[0031] Optionally, the solvent for the hydrolysis-polycondensation reaction of the developer modified with the siloxane reagent and the modified phosphorylcholine polymer modified with the siloxane reagent is a mixture of methanol and water, a mixture of isopropanol and water, or a mixture of DMSO and water.

[0032] Optionally, the siloxane reagent-modified developer is prepared by the following preparation method:

[0033] reacting a developer with a siloxane reagent in a mixed solvent to obtain a developer modified with the siloxane reagent;

[0034] Optionally, the molar ratio of the developer to the siloxane reagent is 1:1 to 3:1, for example 1:1, 1.5:1, 1.8:1, 2:1, 2.3:1, 2.5:1, 2.8:1 or 3:1.

[0035] Optionally, the developer and the siloxane reagent are reacted at room temperature, and the reaction time is 3 to 12 hours, such as 3 hours, 5 hours, 8 hours, 10 hours, 11 hours or 12 hours, and may be 6 hours.

[0036] Optionally, the mixed solvent is a mixture of methanol and water, a mixture of isopropanol and water, or a mixture of DMSO and water, and the volume ratio of the two solvents in the mixed solvent can be 1:1.

[0037] Optionally, the siloxane-modified modified phosphorylcholine polymer has the following structure:

[0038] wherein m=1-40 (e.g., 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40, etc.), n=1-40 (e.g., 1, 2, 3, 5, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30, 32, 34, 36, 38, or 40, etc.), k=1-3 (e.g., 1, 2, or 3), and R is selected from a C1-C5 alkyl group or a C1-C5 alkylsilyl group.

[0039] Optionally, the siloxane-modified modified phosphorylcholine polymer is prepared by the following preparation method:

[0040] 2-Methacryloyloxyethyl phosphorylcholine reacts with a siloxane compound to obtain the siloxane-modified modified phosphorylcholine polymer.

[0041] Optionally, the siloxane compound is methacryloxypropyltris(trimethylsiloxy)silane and / or 3-(methacryloxy)propyltrimethoxysilane.

[0042] Optionally, the molar ratio of the 2-methacryloyloxyethyl phosphorylcholine to the siloxane compound is 40:1 to 10:1, for example, 40:1, 38:1, 35:1, 33:1, 30:1, 28:1, 25:1, 20:1, 18:1, 15:1, 13:1, 10:1, etc.

[0043] Optionally, the reaction of 2-methacryloyloxyethyl phosphorylcholine with the siloxane compound is carried out in the presence of 4-cyano-4-(thiobenzoyl)valeric acid.

[0044] Optionally, the reaction of 2-methacryloyloxyethyl phosphorylcholine with the siloxane compound is carried out in the presence of an initiator.

[0045] Optionally, the initiator is selected from azobisisobutyronitrile.

[0046] Optionally, the reaction temperature of the 2-methacryloyloxyethyl phosphorylcholine and the siloxane compound is 60-70°C, for example, 60°C, 63°C, 65°C, 68°C or 70°C, and the reaction time is 12 to 48 hours, for example, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 24 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours or 48 hours, and can be 24 hours.

[0047] Optionally, the reaction of 2-methacryloyloxyethyl phosphorylcholine with the siloxane compound is carried out in a solvent selected from n-propanol.

[0048] In another aspect, the present application provides use of the novel antifouling developing coating material described above in coating a substrate surface.

[0049] Optionally, the substrate surface includes a silicon-based surface, a glass-based surface, a metal-based surface, or a high-molecular polymer-based surface.

[0050] The material of the present application can be applied to the surfaces of various substrates, including glass substrates, metal substrates and various plastic and polymer substrates (silicone rubber, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, etc.).

[0051] In the present application, the developing functional monomer and the antifouling functional polymer in the novel antifouling developing coating material are connected by a silicon oxide compound, and the silicon oxide compound can be more firmly bonded to the substrate, thereby ensuring the stability and safety of the coating material of the present application on the substrate. Especially in the case of a silicon-based substrate, the silicon oxide compound can be incorporated into the substrate material, or even covalently bonded to the substrate material, to further ensure safety.

[0052] The present application provides a design and preparation concept for a new antifouling developing coating that can be applied to any substrate surface, preferably a silicon-based substrate surface. The structural design principle of its molecular structure is shown in Figure 1. The molecular structure of the new antifouling developing coating material involved in this application mainly includes two parts, namely a developing functional monomer and an antifouling functional polymer. The developing functional monomer uses a compound that can covalently bind to phosphorylcholine, for example, an intermediate molecule obtained by reacting an iodine-containing compound (such as iohexol hydrolyzate) with epoxy silane. The developing functional monomer has excellent X-ray absorption properties and can produce accurate and clear developing effects in medical imaging, providing reliable imaging information for medical angiography. The developing functional monomer is tightly combined with the antifouling polymer modified phosphorylcholine that also contains silane groups through silane hydrolysis polymerization to form a composite structure while maintaining their respective properties. The introduction of the antifouling functional monomer gives the coating excellent antifouling properties, which can effectively inhibit the adhesion of protein bacteria, thereby preventing bacterial infection and cross-infection. In scenarios with high hygiene standards such as medical equipment and catheters, this antifouling property is of great significance to ensure the hygienic safety of medical equipment. Through the combined action of developer-functional monomers and antifouling monomers, the new antifouling developer coating forms a product with silane groups. This covalent bonding ensures exceptional stability on silicon-based surfaces, preventing them from fading or falling off over time, significantly improving the durability and reliability of the developer coating. Furthermore, due to the universality of the silane groups, the coating can be bonded to a variety of substrate surfaces, including glass, metal, and various plastic and polymer substrates (silicone rubber, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, etc.), providing a wide range of applicability and flexibility for the developer coating's applications.

[0053] The design concept of this application's antifouling developer material cleverly combines developer and antifouling functions. By rationally selecting monomers and achieving covalent bonding, the coating possesses both developer and antifouling properties. This design concept is universal and operational, providing a new direction for the research and development and application of medical imaging developer materials, and bringing further progress and breakthroughs to the fields of medical diagnosis and treatment.

[0054] On the other hand, the present application provides an anti-fouling developing coating, wherein the raw materials for preparing the anti-fouling developing coating include the novel anti-fouling developing coating material as described above.

[0055] The mixing mass ratios of the developing functional monomer and the antifouling functional polymer in the novel antifouling developing coating are 2:1, 1:1, and 1:2. In the preparation of the antifouling developing coating, the antifouling developing coating material needs to be dissolved in a solvent (such as n-propanol) so that the concentration of the antifouling developing coating material is 400 mg / mL.

[0056] On the other hand, the present application provides the use of the novel antifouling developing coating material as described above in medical devices or medical materials, optical lenses or industrial printing.

[0057] The coating material of this application can be applied to antifouling and developing functional coatings for medical devices, giving the coated objects both antifouling and X-ray imaging functions. The novel antifouling and developing coating of this application can also be further applied to optical lens coatings and antifouling and developing functional coatings in the field of industrial printing.

[0058] Compared with the related art, this application has the following beneficial effects:

[0059] The antifouling coating prepared on medical devices using the new antifouling developer coating material of this application has excellent antifouling properties and has significantly improved antifouling compared to traditional developer coatings. The coating contains a unique antifouling agent component that effectively resists the adhesion of bacterial proteins and prevents bacterial infection and cross-infection. This feature is crucial to medical safety and ensures the hygiene and safety of medical equipment during use. The improvement of the developer coating makes it suitable for various medical scenarios, especially for equipment such as operating rooms and medical catheters that require high hygiene standards.

[0060] Secondly, this new anti-fouling developing coating exhibits superior developing effects. Compared to traditional developing coatings, it is covalently bonded to the substrate and prevents loss into the body's metabolism, ensuring a stable and long-lasting developing effect. This eliminates potential side effects of developing coatings and improves the safety of medical developing coatings, positively impacting patient health and medical experience.

[0061] Furthermore, the novel antifouling developer coating described in this application is universally applicable. Through silane bond polymerization, the coating can covalently bond to any silicon-based substrate, including glass, silicone sheets, marble, and other silicon-based surfaces. It is widely applicable in various clinical and laboratory scenarios, meeting the needs of diverse users. Its preparation method is simpler and less expensive than traditional coatings, providing a viable path for the large-scale application of developer coatings.

[0062] In summary, the innovation of this new antifouling and developer coating lies in its successful integration of antifouling and developer performance, addressing challenges in this field. Conventional developer coatings often compromise between developer effectiveness and antifouling performance. However, this new coating, through covalent bonding technology, cleverly combines both. This opens up a new direction for the research and development of medical developer materials and provides more innovative solutions. The new antifouling and developer coating excels in antifouling performance, developer effectiveness, universality, and innovation. Its superior performance holds broad application prospects in medical imaging, providing strong support for the safety of medical devices and the accuracy of medical images. Through continued research and innovation, we believe that this new antifouling and developer coating will bring further advancements and breakthroughs to medical diagnosis and treatment.

[0063] Still other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] The accompanying drawings are used to provide a further understanding of the technical solution of this article and constitute a part of the specification. Together with the embodiments of this application, they are used to explain the technical solution of this article and do not constitute a limitation on the technical solution of this article.

[0065] FIG1 is a schematic diagram showing the design principle of a novel antifouling developing coating;

[0066] FIG2 is a NMR test result of a developer compound used to prepare a novel antifouling developer coating;

[0067] FIG3 is an X-ray photoelectron spectroscopy test result of the developer compound used to prepare the novel antifouling developer coating;

[0068] FIG4 is a comparative example of the development of molecular NMR spectra of sodium diatrizoate combined with aminosilane;

[0069] FIG5 is a comparative example of the development of molecular NMR spectra of ioversol combined with 3-glycidyloxypropyltrimethoxysilane;

[0070] FIG6 is an NMR spectrum of a developing molecule obtained by combining iohexol and isocyanate silane via an ester bond;

[0071] FIG7A is a diagram showing the development effect of the novel anti-fouling developing coating;

[0072] FIG7B is a graph showing the quantitative analysis results of the grayscale value of the developing effect of the novel anti-fouling developing coating;

[0073] FIG8A is a fluorescence microscopy image of the novel anti-fouling developing coating against protein adhesion;

[0074] FIG8B is a graph showing the results of fluorescence quantitative analysis of the anti-protein adhesion of the novel anti-fouling developing coating;

[0075] FIG9A is a SEM image of the antibacterial adhesion test results of the novel antifouling developing coating;

[0076] FIG9B is a graph showing the results of a quantitative analysis of the anti-bacterial adhesion of the novel anti-fouling developing coating;

[0077] FIG10A is a graph showing the development test results of the novel antifouling developing coating inside rat and pork tissues;

[0078] FIG10B is a diagram showing quantitative analysis of the development of the novel antifouling developing coating inside rat tissue;

[0079] FIG10C is a diagram showing the quantitative analysis results of the development of the new antifouling development coating inside pork tissue. DETAILED DESCRIPTION

[0080] The following will be combined with the specific embodiments and drawings of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0081] In the description of this application, it should be noted that the terms "upper," "lower," "inner," "outer," "front end," "rear end," "both ends," "one end," "the other end," and the like, indicating positions or relationships, are used solely to facilitate the description of this application and simplify the description. They do not indicate or imply that the devices or components referred to must have a specific orientation, be constructed, or operate in a specific orientation. Therefore, they should not be construed as limitations on this application. Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0082] In the description of this application, it should be noted that, unless otherwise expressly specified or limited, the terms "installed," "provided with," "connected," etc. should be understood broadly. For example, "connected" may refer to a fixed connection, a detachable connection, or an integral connection; it may also refer to an indirect connection through an intermediate medium, such as internal communication between two components. Those skilled in the art will understand the specific meanings of the above terms in this application based on the specific circumstances.

[0083] Example 1 Synthesis example of modified phosphorylcholine.

[0084] 2-Methacryloxyethylphosphocholine (3g), 4-cyano-4-(thiobenzoyl)valeric acid (3g), and azobisisobutyronitrile (0.16g) were dissolved in n-propanol (100ml). Under nitrogen, the temperature was slowly raised to 65°C and stirred for 24 hours. Methacryloxypropyltris(trimethylsiloxy)silane (8ml) was then added and the reaction continued for 24 hours. The resulting n-propanol solution was added to diethyl ether (200ml) for precipitation and filtered and dried to obtain a phosphorylcholine polymer.

[0085] Example 2 Preparation Example of New Antifouling Developing Coating Material

[0086] a) Dissolve iohexol hydrolyzate (5 g) in 10 ml of a 1:1 methanol / water binary mixed solvent, then add potassium hydroxide (1.67 g) and stir under room temperature and ultrasonicate to fully dissolve to obtain a light yellow solution; (2g) was dissolved in 10ml of a methanol / water binary mixed solvent, which was then mixed with the light yellow solution and stirred at room temperature overnight. The product after the reaction was then extracted from the methanol / water binary solvent into the organic phase using ethyl acetate, and the extraction was repeated 5 times. The reaction mixture was then evaporated using a rotary evaporator to remove the organic solvent, and then dialyzed and liquid phase treated to obtain the silicon-modified developing functional monomer C. 27 H 44 I3N3O 13 Si.

[0087] b) The developer-functional monomer from step (a) was mixed with modified phosphorylcholine at varying molar ratios (i.e., 2:1, 1:1, and 1:2) in a methanol / water binary solvent (methanol / water volume ratio of 1:1). The mixture was stirred at room temperature for 6 hours to allow for complete hydrolysis and polymerization of the silyl groups of the modified phosphorylcholine antifouling molecule. The resulting antifouling developer polymer was then purified by organic solvent extraction and rotary evaporation to yield the antifouling developer polymer (Figure 1).

[0088] Example 3 Tests of the present application in terms of basic characterization of compounds

[0089] In order to determine whether the new antifouling developing materials were successfully synthesized and their elemental composition, we performed H NMR spectroscopy ( 1HNMR (deuterated chloroform) and X-ray photoelectron spectroscopy (XPS) tests were performed. As shown in Figure 2, the H NMR spectrum curve exhibits vibration peaks at 7.3ppm and 3.55ppm, corresponding to the iodophenyl group in the developer monomer and the siloxane group in the antifouling molecule, respectively, demonstrating the successful synthesis of the antifouling developer polymer material. As shown in Figure 3, the XPS curve detects peaks at 285eV, 532eV, 400eV, and 620eV, corresponding to the elements C, O, N, and I, respectively. Furthermore, as the proportion of the iodine-containing developer monomer increases, the I content of the sample increases from 2.59% to 4.2%, demonstrating the successful polymerization of the iodine-containing developer monomer and the antifouling molecule-modified phosphorylcholine.

[0090] Example 4

[0091] a) Sodium diatrizoate (5g) was dissolved in 10ml of a 1:1 ethanol / water mixture. O-benzotriazole-tetramethyluronium hexafluorophosphate (0.85g) and triethylamine (600μl) were then added and stirred at room temperature under sonication to fully dissolve the mixture, yielding a colorless solution. (3-Aminopropyl)triethoxysilane (2g) was dissolved in 10ml of ethanol, mixed with the colorless solution, and stirred at room temperature overnight. The reaction product was then extracted into the organic phase with ethyl acetate, and the extraction was repeated five times. The reaction mixture was then evaporated on a rotary evaporator to remove the organic solvent. After dialysis and liquid phase treatment, the imaging molecule of sodium diatrizoate and aminosilane was obtained. The resulting molecular NMR data are shown in Figure 4.

[0092] b) The developer molecule in a) and modified phosphorylcholine were mixed in different ratios (i.e., 2:1, 1:1, and 1:2) in a methanol / water binary solvent (methanol / water volume ratio was 1:1), and hydrolyzed and polymerized to synthesize an anti-fouling developer polymer.

[0093] Example 5

[0094] a) Ioversol (5g) was dissolved in 10mL of a methanol / water binary mixed solvent (1:1), and potassium hydroxide (1.67g) was added and stirred at room temperature and ultrasonicated to fully dissolve it to obtain a light yellow solution; 3-glycidyloxypropyltrimethoxysilane (2g) was dissolved in 10mL of a methanol / water binary mixed solvent, and then mixed with the light yellow solution and stirred at room temperature overnight. The reaction product was then extracted from the methanol / water binary solvent into an organic phase with ethyl acetate, and the extraction was repeated 5 times. The reaction mixture was then evaporated on a rotary evaporator to remove the organic solvent, and then dialyzed and liquid-phase treated to obtain a developer-functional monomer. The NMR data are shown in Figure 5.

[0095] b) The developer molecule in a) and modified phosphorylcholine were mixed in different ratios (i.e., 2:1, 1:1, and 1:2) in a methanol / water binary solvent (methanol / water volume ratio was 1:1), and hydrolyzed and polymerized to synthesize an anti-fouling developer polymer.

[0096] Comparative Example 1

[0097] Iohexol (5g) was dissolved in 10ml of a 1:1 methanol / water mixture, followed by the addition of potassium hydroxide (1.67g) with stirring and sonication at room temperature to fully dissolve the mixture, yielding a pale yellow solution. 3-Isocyanatopropyltriethoxysilane (2g) was dissolved in 10ml of a 1:1 methanol / water mixture, mixed with the pale yellow solution, and stirred overnight at room temperature. The product was then extracted from the methanol / water mixture into the organic phase using ethyl acetate, repeated five times. The reaction mixture was then evaporated on a rotary evaporator to remove the organic solvent. After dialysis and liquid phase treatment, the isocyanate-alcoholic hydroxyl group reacted to form a developing functional monomer, as shown in Figure 6. Due to the change in linkage from a silane bond to an ester bond, the ester bond is unstable and easily hydrolyzed, resulting in a shift in the NMR peaks.

[0098] Example 6 Test on the developing effect of the anti-fouling and developing polymer coating synthesized with different proportions of components in this application.

[0099] In terms of development effect, a medical x-ray irradiator was used to test the development effect of the antifouling development coating. The control group was a blank negative control and a platinum metal ring positive control. The ratio of different raw material components was adjusted to optimize the development effect of the coating. As shown in Figures 7A and 7B, the mass ratios of the development molecule iohexol and the antifouling molecule modified phosphorylcholine in the experimental group were 2:1, 1:1, and 1:2, respectively. As can be seen from Figure 7A, the development performance is significantly enhanced as the proportion of iohexol increases, and when the proportion of iohexol is high, the development performance is comparable to that of platinum metal, indicating that the development performance of the antifouling development coating is excellent and can be clearly imaged under x-rays. Afterwards, imageJ software was used to quantitatively analyze the grayscale value of the coating development effect (Figure 7B). The control group was a blank negative control and a platinum metal ring positive control. As shown in Figure 7B, the development grayscale value is proportional to the iohexol content. When the component ratio is 4:1, the grayscale value is the largest, the development effect is the best, and the development performance is comparable to that of the platinum metal ring.

[0100] Example 7 Test of the anti-fouling and developable polymer coating against protein adhesion in this application.

[0101] In terms of protein adsorption resistance, the adsorption capacity of fibrin (FIB), serum protein (HB), and collagen (Col) on the antifouling developer coating was measured and characterized. The antifouling developer coating used a 1:2 ratio of developer molecules to antifouling molecules. The protein molecules used were pre-modified with fluorescent molecules and adsorbed for 21 days. The adsorption of various molecules on the coating was observed using a fluorescence microscope (instrument model: FV3000-Olympus, Japan, manufacturer: Olympus) on days 1, 3, 7, and 21 (labeled as day 1, day 3, day 7, and day 21 in Figure 8B). The control group was a blank control without antifouling developer coating (uncoating in Figures 8A and 8B, and the coated group is represented by coating). As shown in Figure 8A, compared with the blank control, the coating exhibited excellent protein adsorption resistance. Serum protein was hardly adsorbed on the coating, and the amount of fibrin adsorbed on the antifouling developer coating was also very small, while the blank control was covered with adsorbed protein molecules. Furthermore, we performed a fluorescence quantitative analysis of the total amount of adsorbed molecules (Figure 8B). Compared with the blank control group, the total amount of protein adsorbed on the anti-fouling developing coating was significantly reduced, demonstrating the super strong anti-protein adsorption ability of the anti-fouling developing coating.

[0102] Example 6 Test of the anti-bacterial adhesion of the anti-fouling and developable polymer coating in this application.

[0103] In terms of antibacterial adhesion, we used Candida albicans (C. albicans), Escherichia coli (E. coli), and Staphylococcus aureus (S. aureus) to characterize the antibacterial adsorption ability of the antifouling developer polymer coating. The antifouling developer coating used a 1:2 ratio of developer molecules to antifouling molecules. After soaking the samples in a high concentration (108 / mL) of the three bacterial solutions for two weeks, they were removed and air-dried, and the bacterial counts on the samples were observed using SEM. The bacterial solution was a live bacterial solution, and the solvent was a dialysate. The live bacteria were replaced every three days to ensure bacterial activity. As shown in Figure 9A, after two weeks of adsorption by the three different bacteria, the control group without the antifouling developer coating showed obvious large colonies, while the samples coated with the antifouling developer coating showed no significant colony growth. Further, we conducted a quantitative analysis of the adsorbed colonies (Figure 9B). The samples coated with the antifouling developer coating significantly reduced bacterial adhesion, with the amount of bacteria adhering decreasing by 95% after two weeks.

[0104] Example 7 Development test of the antifouling and developing polymer in this application inside rat and pork tissues.

[0105] The antifouling developing coating was coated on a silicone catheter with a diameter of 0.5 mm, and the catheter was inserted into the rat and pork tissues. A medical X-ray irradiator (manufacturer: Frame View Core; model: XVS2530) was used to photograph the side and front of the rat and pork. The control group was a blank negative control, and the mass ratios of the developing molecule iohexol to the antifouling molecule modified phosphorylcholine in the experimental group were 2:1, 1:1, and 1:2, respectively. As shown in Figure 10A, the developing antifouling coating had a significant developing effect inside the rat and pork tissues, and clear images were obtained under the x-ray irradiator. As shown in Figures 10B and 10C, quantitative analysis of the developing part by Image J software revealed that the developing intensity inside the rat and pork was significantly enhanced as the proportion of iohexol increased.

[0106] The applicant declares that while the aforementioned embodiments are used to illustrate the novel anti-fouling developing coating material, its preparation method, and its application, this application is not limited to these embodiments, nor does it imply that this application must rely on these embodiments in order to be implemented. Persons skilled in the art should understand that any improvements to this application, equivalent substitutions for the raw materials used, addition of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of this application.

Claims

1. An antifouling developing coating material, wherein: The anti-fouling developing coating material has a structure as described in Formula I below: Among them, m=1~40, n=1~40, k=1~3.

2. The antifouling developing coating material according to claim 1, wherein: The developer is one selected from iohexol, iohexol hydrolyzate, iopromide, diatrizoate, sodium diatrizoate, iodized oil and iodixanol, or a mixture of at least two of them, and may be iohexol or iohexol hydrolyzate.

3. The antifouling developing coating material according to claim 1 or 2, wherein: The developer and the siloxane are connected via a connecting group.

4. The antifouling developing coating material according to any one of claims 1 to 3, wherein: The developer and siloxane are connected by forming a Si-O-Si bond.

5. The antifouling developing coating material according to any one of claims 1 to 4, wherein: The antifouling developing coating material has the following structure: Wherein, m=1-40, n=1-40, k=1-3, R is selected from C1-C5 alkyl or C1-C5 alkylsilyl, L is 6. The antifouling developing coating material according to any one of claims 1 to 5, wherein: m:n=1:1~4:1, and m:n=3:1 can be selected.

7. The method for preparing the antifouling developing coating material according to any one of claims 1 to 6, comprising the following steps: The developer modified by siloxane reagent is subjected to hydrolysis and polycondensation reaction with the modified phosphorylcholine polymer modified by siloxane to obtain the novel antifouling developing coating material.

8. The preparation method according to claim 7, wherein: The siloxane agent is selected from One or a combination of at least two of 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

9. The preparation method according to claim 7 or 8, wherein: The molar ratio of the developer modified by the siloxane reagent to the modified phosphorylcholine polymer modified by the siloxane is 40:1 to 10:

1.

10. The preparation method according to any one of claims 7 to 9, wherein: The hydrolysis and polycondensation reaction of the developer modified by the siloxane reagent and the modified phosphorylcholine polymer modified by the siloxane is carried out at room temperature, and the reaction time is 12 to 48 hours; Optionally, the solvent for the hydrolysis-polycondensation reaction of the developer modified by the siloxane reagent and the modified phosphorylcholine polymer modified by the siloxane reagent is a mixture of methanol and water, a mixture of isopropanol and water, or a mixture of DMSO and water.

11. The preparation method according to any one of claims 7 to 10, wherein: The developer modified by the siloxane reagent is prepared by the following preparation method: reacting a developer with a siloxane reagent in a mixed solvent to obtain a developer modified with the siloxane reagent; Optionally, the molar ratio of the developer to the siloxane reagent is 1:1 to 3:1, and may be 2:1; Optionally, the temperature of the reaction of the developer and the siloxane reagent is room temperature, and the reaction time is 3h to 12h, and optionally 6h; Optionally, the mixed solvent is a mixture of methanol and water, a mixture of isopropanol and water, or a mixture of DMSO and water.

12. The preparation method according to any one of claims 7 to 11, wherein: The siloxane-modified modified phosphorylcholine polymer has a structure shown in the following formula III: Wherein, m=1-40, n=1-40, k=1-3, and R is selected from a C1-C5 alkyl group or a C1-C5 alkylsilyl group.

13. Use of the novel antifouling developing coating material according to any one of claims 1 to 6 in coating a substrate surface; Optionally, the substrate surface includes a silicon-based surface, a glass-based surface, a metal-based surface, or a high-molecular polymer-based surface.

14. An antifouling developing coating, wherein: The raw materials for preparing the anti-fouling developing coating include the novel anti-fouling developing coating material according to any one of claims 1 to 6.

15. Use of the novel antifouling developing coating material according to any one of claims 1 to 6 in medical devices or medical materials, optical lenses or industrial printing.

Images