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

By introducing modified phosphocholine polymers with barium ions combined with sulfonate into the developing coating, the contradiction between development and anti-fouling performance is solved, and the stability and anti-fouling performance of the developing coating are improved. It is suitable for a variety of substrates, especially in medical imaging to provide clear and safe development effects.

WO2025138778A1PCT designated stage expired Publication Date: 2025-07-03SUZHOU SILVER MARS NEW MATERIALS TECHNOLOGY CO LTD
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Patent Information

Application Number
PCT/CN2024/108527
Authority / Receiving Office
WO · WO
Patent Type
Applications
Current Assignee / Owner
Priority Date
2024-06-28
Filing Date
2024-07-30
Publication Date
2025-07-03

AI Technical Summary

Technical Problem

There is a contradiction between the development and anti-fouling performance of existing medical development coatings, and it is difficult to achieve excellent development and anti-fouling performance at the same time, affecting the clarity and safety of medical images.

Method used

The stability and bondability of antifouling and development are ensured by combining barium ions with sulfonate into a modified phosphocholine polymer modified by silicone and sulfonate.

Benefits of technology

The stability and durability of the developing coating are achieved, the antifouling performance is significantly improved, the adhesion between bacteria and proteins is reduced, and the stability and safety of the development effect is ensured. It is suitable for a variety of substrates and is widely used in medical imaging.

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Patent Text Reader

Abstract

A new antifouling developing coating material, and a preparation method therefor and the use thereof. In the antifouling developing coating material, barium ions are combined with the sulfonate anions, and the barium ions are introduced into the structure of a modified choline phosphate polymer, which is modified with siloxane and sulfonate anions, thereby allowing the material to have combined antifouling and developing functions; therefore, the stability of the material is ensured, and the material has wide application prospects in the field of medical imaging.
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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 vital role in medical imaging. With the continuous advancement of medical imaging, the requirements for developer coatings are also increasing. In addition to excellent developer performance, they must also possess excellent antifouling properties to resist bacterial protein adhesion, prevent infection, and maintain a clean and transparent surface to ensure clear and accurate images.

[0003] The development of medical antifouling coatings stems from improvements to traditional developing coatings. While these coatings provide developing functionality, their antifouling properties are limited. With the increasing use of medical devices, scientists are urgently looking to add antifouling materials to enhance their antifouling properties. Antifouling principles primarily involve the hydrophilicity and lipophilicity of a material's surface. Hydrophilic surfaces create a high contact angle for water, preventing the retention of water and impurities, while hydrophobic surfaces prevent the adhesion of organic matter and oils, reducing the adsorption of biomolecules. Recent research in medical antifouling coatings has made significant progress. By tailoring surface properties, superior antifouling coatings have been developed. For example, the introduction of superhydrophobic polymers can impart a superhydrophobic effect to surfaces, achieving 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 contaminants. Furthermore, embedding bioactive molecules into the coating to form a "sterilization zone" can inhibit microbial growth and enhance antifouling effectiveness.

[0004] The developing performance of medical anti-fouling developer coatings has a crucial impact on the clarity of medical images and the accuracy of diagnosis. The developer coating needs to be sensitive to X-rays to ensure good developing effects under X-ray irradiation. Development technology is widely used in medical imaging, and clear images are produced through the development of image-sensitive materials. Among them, X-ray development is a commonly used technology that relies on the absorption and scattering of X-rays. The developer coating plays a key role in this process, producing images by absorbing and scattering X-rays. The research on medical developer coatings has made continuous progress with the continuous advancement of medical imaging technology. Researchers have improved the development efficiency and image quality by improving the chemical composition of developers and coatings.

[0005] However, the interaction between the developer and the antifouling agent may reduce the development efficiency, so the effective combination of development and antifouling functions remains a challenging problem that needs to be solved.

[0006] Summary of the Invention

[0007] 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.

[0008] The present application provides a novel anti-fouling developing coating material and a preparation method and application thereof.

[0009] In one aspect, the present application provides a novel anti-fouling and developing coating material, wherein the anti-fouling and developing coating material has a structure as shown in the following formula I:

[0010] wherein m=20, n=10, k=3, R1 and R2 are siloxane-containing groups, and R1 and R2 are the same or different.

[0011] The antifouling and developing coating material described in the present application introduces barium ions into the structure of a modified phosphorylcholine polymer modified with siloxane and sulfonate groups through the combination of barium ions and sulfonate groups, so that the resulting material combines antifouling and developing properties, ensuring the stability of the material and the stability of the antifouling and developing properties. The material has outstanding performance in both antifouling 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.

[0012] 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.

[0013] In some optional embodiments, R1 and R2 are independently selected from tris(trimethylsiloxy)silyl or trimethoxysilyl, the structures of which are as follows:

[0014] In the present application, m, n and k represent the number of structural units, wherein R1 in n structural units may be the same or different, and R2 in n structural units may be the same or different.

[0015] 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:

[0016] (1) preparing a modified phosphorylcholine polymer modified with siloxane and sulfonate;

[0017] (2) adding the barium salt to the solution containing the modified phosphorylcholine polymer modified with siloxane and sulfonate, reacting to obtain the novel antifouling developing coating material.

[0018] Optionally, the step (1) specifically includes the following steps: 2-methacryloyloxyethyl phosphorylcholine reacts with a siloxane compound and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide to obtain the modified phosphorylcholine polymer modified with siloxane and sulfonate.

[0019] Optionally, the siloxane compound is methacryloxypropyltris(trimethylsiloxy)silane, methacryloxypropyltris(trimethoxy)silane or vinyltrimethoxysilane.

[0020] Optionally, the molar ratio of the 2-methacryloyloxyethyl phosphorylcholine to the siloxane compound is 1:1-8:1, for example, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1 or 8:1.

[0021] Optionally, the reaction of 2-methacryloyloxyethyl phosphorylcholine with the siloxane compound is carried out in the presence of 4-cyano-4-(thiobenzoyl)valeric acid.

[0022] Optionally, the molar ratio of 2-methacryloyloxyethyl phosphorylcholine to 4-cyano-4-(thiobenzoyl)pentanoic acid is 1:1-5:1, for example 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1.

[0023] Optionally, the reaction of 2-methacryloyloxyethyl phosphorylcholine with the siloxane compound is carried out in the presence of an initiator.

[0024] Optionally, the initiator is selected from azobisisobutyronitrile.

[0025] Optionally, the molar ratio of the 2-methacryloyloxyethyl phosphorylcholine to the initiator is 1:1-5:1, for example 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1.

[0026] Optionally, the molar ratio of 2-methacryloyloxyethyl phosphorylcholine to (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide is 2:1-8:1, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1 or 8:1.

[0027] Optionally, the reaction temperature in step (1) is 60°C-70°C (e.g., 60°C, 63°C, 65°C, 68°C or 70°C), and the reaction time is 16-64h (e.g., 16h, 18h, 20h, 24h, 28h, 30h, 36h, 40h, 42h, 48h, 50h, 55h, 58h, 60h or 64h).

[0028] Optionally, the solvent for the reaction in step (1) is one or a mixture of at least two of n-propanol, methanol, acetone, tetrahydrofuran, n-butanol and isopropanol.

[0029] Optionally, the reaction in step (1) is carried out under nitrogen protection.

[0030] Optionally, a more specific operation of step (1) is as follows: 2-methacryloyloxyethyl phosphorylcholine, 4-cyano-4-(thiobenzoyl)valeric acid, and azobisisobutyronitrile are dissolved in n-propanol, heated to 60°C-70°C under nitrogen protection, stirred and reacted for 16-32 hours, and then a siloxane compound and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide are added, and the reaction is continued for 16-32 hours to obtain the modified phosphorylcholine polymer modified with siloxane and sulfonate.

[0031] Optionally, after the reaction in step (1) is completed, a post-treatment step is further included, wherein the post-treatment step is to precipitate the obtained reaction solution in ether, filter and dry it.

[0032] In the present application, the barium salt in step (2) is selected from one or a mixture of at least two of barium chloride, barium sulfate, barium nitrate or barium carbonate.

[0033] Optionally, the barium salt is barium chloride.

[0034] Optionally, the molar ratio of the modified phosphorylcholine polymer modified with siloxane and sulfonate to the added amount of the barium salt in step (2) is in the range of 1:1 to 4:1, for example, 1:1, 1.5:1, 1.8:1, 2:1, 2.3:, 2.5:1, 2.8:1, 3:1, 3.3:, 3.5:1, 3.8:1 or 4:1, and can be optionally 1:1.

[0035] Optionally, the solvent in the solution in step (2) is a mixed solvent of methanol and water.

[0036] Optionally, the reaction in step (2) is carried out at room temperature, and the reaction time is 6 to 12 h, for example, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h or 12 h.

[0037] In another aspect, the present application provides use of the novel antifouling developing coating material described above in coating a substrate surface.

[0038] Optionally, the substrate surface includes a silicon-based surface, a glass-based surface, a metal-based surface, or a high-molecular polymer-based surface.

[0039] 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.).

[0040] The new anti-fouling developing coating material of the present application has universal applicability. It combines with the hydroxyl groups on the surface of the substrate through silicon-oxygen bonds and can be covalently bonded to any silicon-based substrate, including various silicon-based surfaces such as glass, silicone sheets, and marble. It combines with other substrate surfaces through hydrophobic effects or van der Waals forces, and is widely applicable to different clinical and laboratory scenarios to meet the needs of different users.

[0041] 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.

[0042] 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.

[0043] Compared with the related art, this application has the following beneficial effects:

[0044] First of all, the new antifouling developing coating material of this application has been successfully applied to medical devices, forming an antifouling coating with excellent antifouling properties. Compared with traditional developing coatings, it has achieved significant improvement in antifouling. The material contains modified phosphorylcholine polymer as a unique antifouling agent component, which can effectively resist the attachment of bacterial proteins and prevent bacterial infection and cross-infection. This feature is crucial to medical safety, ensuring that medical equipment remains hygienic and safe during use. It can be applied to various medical scenarios, especially for equipment requiring high hygiene standards such as operating rooms and medical catheters. It is of special importance.

[0045] Secondly, the new anti-fouling developing coating material of the present application exhibits excellent developing effect. Compared with traditional methods, its surface is in the form of an elastomeric coating that is insoluble in water and will not be lost into the human body's own metabolism, ensuring the stability and durability of the developing effect, thereby eliminating the side effects that may be caused by the developing coating and improving the safety of the medical developing coating, which has positive significance for the patient's health and medical experience.

[0046] In addition, the new anti-fouling developing coating material of the present application is universal. It can be covalently bonded to any silicon-based substrate through silicon-oxygen bonds and the hydroxyl groups on the surface of the substrate, including various silicon-based surfaces such as glass, silicone sheets, and marble. It can be bonded to other substrate surfaces through hydrophobic effects or van der Waals forces, and is widely applicable to different clinical and laboratory scenarios to meet the needs of different users. Its preparation method is simpler and lower in cost than traditional coatings, providing a feasible path for large-scale application of developing coatings.

[0047] Still other aspects will become apparent upon reading and understanding the accompanying drawings and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] 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.

[0049] FIG1 is an NMR data diagram of a modified phosphorylcholine polymer obtained by reacting a mixture of methacryloxypropyl tris(trimethylsiloxy)silane and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide;

[0050] FIG2 is a comparison of the NMR data of the modified phosphorylcholine polymer obtained by reacting a mixture of n-hexyltriethoxysilane and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide with the polymer in Example 1;

[0051] FIG3 is a microscopic morphology of the novel antifouling developing coating material of the present application coated on different substrates, wherein A is a photograph of the coating on a glass sheet, B is a photograph of the coating on a silicone sheet, C is a photograph of the coating on a polyurethane sheet, and D is a photograph of the coating on the tip of a stainless steel syringe needle. The arrows in each photograph point to the edge of the coating;

[0052] FIG4A is a fluorescence microscope photograph of the anti-protein adhesion test results of the novel anti-fouling developing coating material of the present application;

[0053] FIG4B is a graph showing the results of fluorescence quantitative analysis of the total amount of protein molecules adsorbed by the novel anti-fouling and developing coating material of the present application;

[0054] FIG5A and FIG5B are graphs showing the results of an antibacterial adhesion test of the novel antifouling developing coating material of the present application; FIG5A is a photograph showing the results of the antibacterial adhesion test; FIG5B is a graph showing the results of a quantitative analysis of the adsorbed bacterial colonies;

[0055] FIG6A and FIG6B are graphs showing the results of an anti-platelet adhesion test of the novel anti-fouling developing coating material of the present application; FIG6A is a photograph showing the results of the anti-platelet adhesion test; and FIG6B is a graph showing the results of a quantitative analysis of the number of adhered platelets;

[0056] Figures 7A and 7B are X-ray development images of the substrate after the new anti-fouling development coating material of the present application is coated; Figure 7A is an X-ray development photo of different development methods; Figure 7B is a normalized development intensity analysis diagram. DETAILED DESCRIPTION

[0057] The technical solution of the present application is further described below through specific implementation methods. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0058] Example 1

[0059] This embodiment provides a novel anti-fouling developing coating material, which is prepared by a method comprising the following steps:

[0060] 1) 0.75 mol of 2-methacryloyloxyethyl phosphorylcholine, 0.4 mol of 4-cyano-4-(thiobenzoyl)valeric acid, and 0.4 mol of azobisisobutyronitrile were dissolved in n-propanol. The temperature was slowly raised to 65° C. under nitrogen protection and stirred for 24 hours. Then, a mixture of 0.125 mol of methacryloyloxypropyltris(trimethylsiloxy)silane and 0.075 mol of (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide was added and the reaction was continued for 24 hours. The resulting n-propanol solution was added to diethyl ether for precipitation, and filtered and dried to obtain a modified phosphorylcholine polymer. The reaction is shown below. The NMR results of the polymer are shown in Figure 1.

[0061] 2) Barium chloride was dissolved in double-distilled water to a concentration of 200 mg / ml, and then mixed with 600 mg / ml of a modified phosphorylcholine polymer in a methanol / water binary solvent to a total concentration of 400 mg / ml. The mixture was stirred thoroughly at room temperature for 6 hours to allow the barium ions to bind to the sulfonic acid groups of the modified phosphorylcholine polymer, thereby forming an anti-fouling and developing polymer, or anti-fouling and developing coating material, that can be applied to any silicon-based substrate. The molecular structure of the anti-fouling and developing coating material is as follows:

[0062] Among them, m=20, n=10, k=3.

[0063] Example 2

[0064] 1) 0.75 mol of 2-methacryloyloxyethyl phosphorylcholine, 0.4 mol of 4-cyano-4-(thiobenzoyl)valeric acid, and 0.4 mol of azobisisobutyronitrile were dissolved in n-propanol, and the temperature was slowly raised to 65° C. under nitrogen protection, and the reaction was stirred for 24 hours. Then, 0.125 mol of vinyltrimethoxysilane and 0.075 mol of (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide mixture were added, and the reaction was continued for 24 hours. The obtained n-propanol solution was added to diethyl ether for precipitation, and the modified phosphorylcholine polymer was filtered and dried. The NMR results of the polymer were compared with those of the polymer in Example 1, as shown in Figure 2.

[0065] 2) Barium chloride was dissolved in double-distilled water to a concentration of 200 mg / ml, and then mixed with 600 mg / ml of a modified phosphorylcholine polymer in a methanol / water binary solvent to a total concentration of 400 mg / ml. The mixture was stirred thoroughly at room temperature for 6 hours to allow the barium ions to bind to the sulfonic acid groups of the modified phosphorylcholine polymer, thereby forming an anti-fouling and developing polymer, or anti-fouling and developing coating material, that can be applied to any silicon-based substrate. The molecular structure of the anti-fouling and developing coating material is as follows:

[0066] Among them, m=20, n=10, k=3.

[0067] Example 3

[0068] The antifouling developer coating material of Example 1 was applied to glass sheets, silicone sheets, polyurethane sheets, and stainless steel syringe needle tips. The morphology was observed using a scanning electron microscope (S-3400N). The results are shown in Figure 3, where A is a SEM photograph of the coating on a glass sheet, B is a SEM photograph of the coating on a silicone sheet, C is a SEM photograph of the coating on a polyurethane sheet, and D is a SEM photograph of the coating on a stainless steel syringe needle tip. It can be seen that the overall surface of the antifouling developer polymer-coated area is smooth, with a clear boundary from the uncoated area. The coated area has no obvious defects or cracks, demonstrating the stability of the antifouling developer material of this application when applied to different substrates.

[0069] Example 4

[0070] The anti-fouling developing coating material of Example 1 was used to perform an anti-protein adhesion test. In terms of anti-protein adsorption, the adsorption capacity of fibrin (FIB), serum protein (HB) and collagen (Col) on the anti-fouling developing coating was measured and characterized. The protein molecules were fluorescently labeled in advance, and an adsorption experiment was carried out for 21 days. On the 3rd, 14th and 21st days, a fluorescence microscope (Nikon Eclipse TE / Ti) was used to observe the adsorption of various molecules on the coating. The control group was a blank control without an anti-fouling developing coating. The results are shown in Figures 4A and 4B (the 3rd, 14th and 21st days in the figure are marked as day3, day14 and day21 respectively, uncoating means uncoated, coating means coated, and have the same meaning in the following figure).

[0071] As shown in Figure 4A, the coating exhibited excellent protein resistance compared to the blank control. Serum proteins were barely adsorbed on the coating, and the amount of fibrin adsorbed on the anti-fouling and developing coating was also minimal, whereas the blank control was filled with adsorbed protein molecules. Furthermore, fluorescence quantitative analysis of the total amount of adsorbed molecules was performed. As shown in Figure 4B, the total amount of protein adsorbed on the anti-fouling and developing coating was significantly reduced compared to the blank control, demonstrating the coating's strong protein resistance.

[0072] Example 5

[0073] The anti-fouling developer coating material of Example 1 was used to conduct antibacterial adhesion tests. The anti-bacterial adhesion capability of the anti-fouling developer coating was characterized using Candida albicans (C. albicans), Escherichia coli (E. coli), and Staphylococcus aureus (S. aureus). The samples were immersed in a high-concentration (108 / mL) solution of three live bacteria, with the live bacteria replaced every three days. After soaking for two weeks, the samples were removed and air-dried, and the bacterial counts observed using a scanning electron microscope (SEM). The solvent was dialysate to ensure bacterial activity, and the control group served as a blank control. The results are shown in Figures 5A and 5B.

[0074] As shown in Figure 5A, after two weeks of adsorption of three different bacteria, large colonies were evident on the control sample without the anti-fouling developer coating, while no significant bacterial growth was observed on the sample coated with the anti-fouling developer coating. Furthermore, quantitative analysis of the adsorbed colonies was performed, and the results, shown in Figure 5B, demonstrate that the anti-fouling developer coating significantly reduced bacterial adhesion, with a 95% reduction in bacterial adhesion after two weeks.

[0075] Example 6

[0076] The anti-fouling developing coating material of Example 1 was used to perform an anti-platelet adhesion test. The anti-fouling developing coating was coated on different matrix materials such as NiTi, PVC and TPU, and the platelets were contacted with the materials to be tested, and then washed and observed under a scanning electron microscope (SEM) to study the effect of the anti-fouling developing coating on platelet adhesion. The coating concentrations (solution concentrations) of the experimental groups were 100 mg / mL, 200 mg / mL and 300 mg / mL, respectively, and the control group used a blank negative control. The results are shown in Figures 6A and 6B. As shown in Figure 4A, the anti-fouling developing coating exhibited significant anti-platelet adhesion effects on all three materials. The quantitative analysis of the number of adhered platelets is shown in Figure 6B. It can be seen that as the coating concentration increases, the anti-platelet adhesion effect is significantly enhanced.

[0077] Example 7

[0078] The anti-fouling developing coating material of Example 1 was used to perform an X-ray development test. Barium sulfate solution and the anti-fouling developing coating material of the present application were respectively coated on a rectangular glass substrate, and the coating concentration (solution concentration) was 100 mg / mL. A blank group and a commercial platinum-iridium developing ring were used as controls. The results are shown in Figures 7A and 7B, wherein Figure 7A is an X-ray development photograph of different development methods; Figure 7B is a normalized development intensity analysis diagram; it can be seen that the development effect of the anti-fouling developing coating material of the present application is similar to that of barium sulfate, although slightly lower than that of the commercial platinum-iridium developing ring, but the development effect is much higher than that of the blank control group. This shows that the anti-fouling developing coating material of the present application has an X-ray development effect comparable to that of barium sulfate.

[0079] From the above, it can be seen that the antifouling and developing coating material of the present application has excellent coating performance, antifouling performance and X-ray developing effect.

[0080] The modified phosphorylcholine polymer portion of the antifouling and developing coating material of the present application serves as an antifouling unit, and the bound barium serves as a developing unit, exhibiting both excellent antifouling and developing properties. The siloxane groups in the antifouling units can form covalent bonds with the substrate surface, thereby firmly bonding the coating to the substrate and ensuring the stability and safety of the antifouling and developing coating material of the present application on the substrate. For example, the siloxane groups can covalently bond with silicon-based substrate materials, exhibiting excellent stability and preventing loss or detachment over time, significantly improving the durability and reliability of the developing coating. The siloxane groups can also bond to other substrate surfaces through hydrophobic interactions and van der Waals forces, thus providing flexibility and applicability for a wide range of developing coating applications. The anti-fouling and developing coating material of the present application can be coated on the surfaces of various substrates, including silicon-based substrates (such as glass substrates), metal substrates, and various plastic and polymer substrates (such as silicone rubber, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, etc.), and has a wide range of applicability; it can be used in a wide range of fields, for example, in medical devices, optical lenses and industrial printing. The coating gives the coated object the dual functions of anti-fouling and X-ray imaging, and exhibits excellent X-ray absorption performance during development, especially providing accurate and clear development effects for medical imaging, and providing reliable imaging information for medical imaging.

[0081] The applicant declares that while the above-mentioned embodiments are used to illustrate the anti-fouling developing coating material, its preparation method, and its application, this application is not limited to these embodiments, and does not necessarily rely on these embodiments for implementation. 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. A new type of anti-fouling and developing coating material, wherein, The anti-fouling developing coating material has a structure shown in the following formula I: Where m = 1 - 40, n = 1 - 40, k = 1 - 5, R1 and R2 are siloxane groups, and R1 and R2 are the same or different.

2. The novel anti-fouling and developing coating material according to claim 1, wherein, m:n = 1:1 - 4:

1.

3. The novel anti-fouling and developing coating material according to claim 1 or 2, wherein R1 and R2 are independently selected from tris(trimethylsiloxy)silyl or trimethoxysilyl, and their structures are as follows:

4. The preparation method of the novel anti-fouling and developing coating material according to any one of claims 1 - 3, which comprises the following steps: (1) Prepare a modified phosphocholine polymer modified with siloxane and sulfonate groups; (2) Add a barium salt to a solution containing the modified phosphocholine polymer modified with siloxane and sulfonate groups, and react to obtain the novel anti-fouling and developing coating material.

5. The preparation method according to claim 4, wherein, The step (1) specifically comprises the following steps: 2-methacryloyloxyethylphosphorylcholine reacts with a siloxane compound and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfopropyl)ammonium hydroxide to obtain the modified phosphocholine polymer modified with siloxane and sulfonate groups.

6. The preparation method according to claim 5, wherein, The siloxane compound is methacryloyloxypropyltris(trimethylsiloxy)silane, methacryloyloxypropyltris(trimethoxy)silane or vinyltrimethoxysilane.

7. The preparation method according to claim 5 or 6, wherein The molar ratio of 2-methacryloyloxyethylphosphorylcholine to the siloxane compound is 1:1 - 8:

1.

8. The preparation method according to any one of claims 5-7, wherein The reaction of 2-methacryloyloxyethylphosphorylcholine with the siloxane compound is carried out in the presence of 4-cyano-4-(thiobenzoyl)valeric acid; Optionally, the molar ratio of 2-methacryloyloxyethylphosphorylcholine to 4-cyano-4-(thiobenzoyl)valeric acid is 1:1 - 5:

1.

9. The preparation method according to any one of claims 5-8, wherein, The reaction of 2-methacryloyloxyethylphosphorylcholine with the siloxane compound is carried out in the presence of an initiator; Optionally, the initiator is selected from azobisisobutyronitrile; Optionally, the molar ratio of 2-methacryloyloxyethylphosphorylcholine to the initiator is 1:1 - 5:

1.

10. The preparation method according to any one of claims 5-9, wherein, The molar ratio of 2-methacryloyloxyethylphosphorylcholine to (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfopropyl)ammonium hydroxide is 2:1 - 8:

1.

11. The preparation method according to any one of claims 4-10, wherein, The temperature of the reaction in step (1) is 60°C - 70°C, and the reaction time is 16 - 64 h; Optionally, the solvent for the reaction in step (1) is one or a mixture of at least two of n-propanol, methanol, acetone, tetrahydrofuran, n-butanol and isopropanol; Optionally, the reaction in step (1) is carried out under nitrogen protection; Optionally, a more specific operation of step (1) is: dissolve 2-methacryloyloxyethylphosphorylcholine, 4-cyano-4-(thiobenzoyl)valeric acid, and azobisisobutyronitrile in n-propanol, heat to 60°C - 70°C under nitrogen protection, stir and react for 16 - 32 h, then add the siloxane compound and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfopropyl)ammonium hydroxide, and continue to react for 16 - 32 h to obtain the modified phosphocholine polymer modified with siloxane and sulfonate groups; Optionally, after the reaction in step (1), a post-treatment step is further included, and the post-treatment step is to precipitate the obtained reaction solution in ether, filter and dry.

12. The preparation method according to any one of claims 4-11, characterized in that, The barium salt described in step (2) is selected from one or a mixture of at least two of barium chloride, barium sulfate, barium nitrate or barium carbonate; Optionally, the molar ratio of the modified phosphocholine polymer modified with siloxane and sulfonate group to the addition amount of the barium salt in step (2) ranges from 1:1 to 4:1; it can be optionally 1:1; Optionally, the solvent in the solution described in step (2) is a mixed solvent of methanol and water; Optionally, the reaction in step (2) is carried out at room temperature, and the reaction time is 6-12 h.

13. Application of the novel anti-fouling and developing coating material according to any one of claims 1-3 in coating the surface of a substrate; Optionally, the substrate surface includes a silicon-based surface, a glass substrate surface, a metal substrate surface, and a polymer substrate surface.

14. An anti-fouling developing coating, wherein, The preparation raw materials of the anti-fouling and developing coating include the novel anti-fouling and developing coating material according to any one of claims 1-3.

15. Application of the novel anti-fouling and developing coating material according to any one of claims 1-3 in medical devices or medical materials, optical lenses or industrial printing.

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