An antifouling developing coating material and its preparation method and application

By introducing the combination of barium ions and sulfonate into the medical development coating, modifying the modified phosphocholine polymer, the problem of insufficient antifouling performance in the prior art is solved, the effective combination of development and antifouling is achieved, and the clarity and diagnostic accuracy of medical images are improved.

CN119101422BActive Publication Date: 2025-03-28SUZHOU SILVER MARS NEW MATERIALS TECHNOLOGY CO LTD
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Patent Information

Application Number
CN202410861298.9
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Priority Date
2023-12-27
Filing Date
2024-06-28
Publication Date
2025-03-28
Estimated Expiration
2044-06-28

AI Technical Summary

Technical Problem

The existing medical development coatings have shortcomings in antifouling performance, which are difficult to effectively resist the adhesion of bacterial proteins, affecting the clarity of medical images and diagnostic accuracy.

Method used

By introducing the binding of barium ions to the sulfonate, the barium ions are introduced into the modified phosphocholine polymer modified by silicone and sulfonate to form a material with antifouling and development bond.

Benefits of technology

It has achieved excellent anti-fouling performance and development effects, making the materials have a wide range of application prospects in the field of medical imaging, providing strong support for the safety of medical equipment and the accuracy of medical imaging.

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Abstract

The present invention provides an antifouling developing coating material and a preparation method and application thereof. The antifouling developing coating material has a structure as shown in Formula I. The antifouling developing coating material of the present invention has both excellent antifouling performance and developing performance, can ensure the stability and durability of the developing effect, has good safety, and has a wider range of applications.
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Description

[0001] This application claims priority to patent application number 202311820422.9. The filing date of the prior application is December 27, 2023. The name of the invention is an anti-fouling developing coating material, preparation method and application thereof. Technical Field

[0002] The invention belongs to the technical field of medical materials and relates to an anti-fouling developing coating material and a preparation method and application thereof. Background Art

[0003] 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 function, they must also have excellent anti-fouling properties to resist bacterial protein adhesion, prevent infection, and maintain a clean and transparent surface to ensure clear and accurate images.

[0004] The development of medical antifouling developing coatings stems from the improvement of traditional developing coatings. Although traditional developing coatings can provide developing functions, their antifouling performance is limited. With the increase in the use of medical devices, scientists urgently need to study the addition of antifouling materials to improve the antifouling performance. The antifouling principle mainly includes the hydrophilicity and lipophilicity of the material surface. The hydrophilic surface can make water form a large contact angle to prevent the retention of water and impurities, while the hydrophobic surface can prevent the attachment of organic matter or oils and reduce the adsorption of biological molecules. In recent years, the research on medical antifouling coatings has made significant progress. By adjusting the surface properties, excellent antifouling coatings have been developed. For example, the introduction of super-hydrophobic polymer materials makes the surface present a super-hydrophobic effect, achieving efficient self-cleaning and antifouling. At the same time, through the bionic design of special surface structures, such as micro-nano concave-convex and honeycomb, the surface contact area is reduced and the attachment of pollutants is reduced. In addition, embedding bioactive molecules into the coating to form a "sterilization circle" can inhibit the reproduction of microorganisms and improve the antifouling effect.

[0005] The developing performance of medical antifouling 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 development 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 the developer and coating.

[0006] However, the interaction between the developer and the antifouling agent may reduce the development efficiency, so the effective combination of development and antifouling functions is still a challenging problem that needs to be solved. Summary of the invention

[0007] In view of the deficiencies in the prior art, the object of the present invention is to provide an anti-fouling developing coating material and a preparation method and application thereof.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

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

[0010]

[0011]

[0012] Where m = 20, n = 10, k = 3, R 1 and R 2 is a siloxane group, R 1 and R 2 Same or different.

[0013] The antifouling and developing coating material of the present invention introduces barium ions into the structure of a modified phosphorylcholine polymer modified with siloxane and sulfonate by combining barium ions with sulfonate groups, so that the obtained material combines antifouling and developing, ensures the stability of the material, ensures the stability of the antifouling and developing performances, and makes the material have outstanding performance in both antifouling performance and developing effect, so that it has broad application prospects in the field of medical imaging, and provides strong support for the safety of medical equipment and the accuracy of medical images.

[0014] In some preferred embodiments, m:n=1:1-4:1, for example, 1:1, 2:1, 3:1 or 4:1. In the present invention, the ratio of m:n is within 1:1-4:1, and the polymer material that meets the requirements of development and antifouling can be obtained by adjusting the molar ratio of the modified phosphorylcholine polymer to the barium salt.

[0015] In some preferred embodiments, R 1 and R 2 Independently selected from tris(trimethylsiloxy)silyl or trimethoxysilyl, the structure of which is as follows:

[0016]

[0017] In the present invention, m, n and k represent the number of structural units, wherein for n structural units, R 1Can be the same or different, for n structural units R 2 Can be the same or different.

[0018] In another aspect, the present invention provides a method for preparing the anti-fouling developing coating material as described above, the preparation method comprising the following steps:

[0019] (1) preparing a modified phosphorylcholine polymer modified with siloxane and sulfonate;

[0020] (2) adding a barium salt to a solution containing the modified phosphorylcholine polymer modified with siloxane and sulfonate to react and obtain the antifouling developing coating material.

[0021] Preferably, the step (1) specifically includes the following steps: 2-methacryloyloxyethyl phosphorylcholine reacts with a siloxane compound and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonatepropyl)ammonium hydroxide to obtain the modified phosphorylcholine polymer modified with siloxane and sulfonate.

[0022] Preferably, the siloxane compound is methacryloxypropyl tris(trimethylsiloxy)silane, methacryloxypropyl tris(trimethoxy)silane or vinyl trimethoxysilane.

[0023] Preferably, 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.

[0024] Preferably, the reaction of 2-methacryloyloxyethyl phosphorylcholine with the siloxane compound is carried out in the presence of 4-cyano-4-(thiobenzoyl)valeric acid.

[0025] Preferably, 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.

[0026] Preferably, the reaction of 2-methacryloyloxyethyl phosphorylcholine with the siloxane compound is carried out in the presence of an initiator.

[0027] Preferably, the initiator is selected from azobisisobutyronitrile.

[0028] Preferably, 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.

[0029] Preferably, the molar ratio of 2-methacryloyloxyethyl phosphorylcholine to (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonatepropyl)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.

[0030] Preferably, 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).

[0031] Preferably, 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.

[0032] Preferably, the reaction in step (1) is carried out under nitrogen protection.

[0033] Preferably, the more specific operation of step (1) is: dissolving 2-methacryloyloxyethyl phosphorylcholine, 4-cyano-4-(thiobenzoyl)valeric acid, and azobisisobutyronitrile in n-propanol, heating to 60°C-70°C under nitrogen protection, stirring and reacting for 16-32 hours, then adding a siloxane compound and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, and continuing the reaction for 16-32 hours to obtain the modified phosphorylcholine polymer modified with siloxane and sulfonate.

[0034] Preferably, 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.

[0035] In the present invention, 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.

[0036] Preferably, the barium salt is barium chloride.

[0037] Preferably, the molar ratio of the modified phosphorylcholine polymer modified with siloxane and sulfonate to the barium salt added 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, 2.3:1, 2.5:1, 2.8:1, 3:1, 3.3:1, 3.5:1, 3.8:1 or 4:1, preferably 1:1.

[0038] Preferably, the solvent in the solution in step (2) is a mixed solvent of methanol and water.

[0039] Preferably, 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.

[0040] In another aspect, the present invention provides the use of the antifouling developing coating material as described above in coating a substrate surface.

[0041] Preferably, the substrate surface includes a silicon-based surface, a glass-based surface, a metal-based surface, or a high-molecular polymer-based surface.

[0042] The material of the present invention can be applied to the surfaces of various substrates, including glass substrates, metal substrates and various plastic and high molecular polymer substrates (silicone rubber, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, etc.).

[0043] The anti-fouling developing coating material of the present invention has universal applicability. It can be covalently bonded to any silicon-based substrate by combining with the hydroxyl groups on the surface of the substrate through silicon-oxygen bonds, including various silicon-based surfaces such as glass, silicone sheets, and marble. It can be combined 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.

[0044] In another aspect, the present invention provides an anti-fouling developing coating, wherein the raw materials for preparing the anti-fouling developing coating include the anti-fouling developing coating material as described above.

[0045] In another aspect, the present invention provides use of the antifouling developing coating material as described above in medical devices or medical materials, optical lenses or industrial printing.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] First of all, the antifouling developing coating material of the present invention is successfully applied to medical devices to form an antifouling coating with excellent antifouling performance. 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 property is crucial to medical safety and ensures that medical equipment remains hygienic and safe during use. It can be applied to various medical scenarios, especially for equipment that requires high hygiene standards such as operating rooms and medical catheters. It is of special importance.

[0048] Secondly, the anti-fouling developing coating material of the present invention exhibits an excellent developing effect. Compared with the traditional method, 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.

[0049] In addition, the anti-fouling developing coating material of the present invention has universal applicability. It can be covalently bonded to any silicon-based substrate, including glass, silicone sheets, marble and other silicon-based surfaces, by combining with the hydroxyl groups on the surface of the substrate through silicon-oxygen bonds. It can be combined 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. Its preparation method is simpler and less costly than traditional coatings, providing a feasible path for large-scale application of developing coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is the NMR data of the modified phosphorylcholine polymer obtained by reacting a mixture of methacryloxypropyl tris(trimethylsiloxy)silane and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide.

[0051] Figure 2 This is a comparison chart 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 and the polymer in Example 1.

[0052] Figure 3 The microscopic morphology of the antifouling developing coating material of the present invention coated on different substrates, wherein A is a photo of coating on a glass sheet, B is a photo of coating on a silicone sheet, C is a photo of coating on a polyurethane sheet, and D is a photo of coating on a stainless steel syringe needle tip, and the arrows in each photo point to the edge of the coating;

[0053] Figure 4AA fluorescence microscope photograph of the anti-protein adhesion test result of the anti-fouling developing coating material of the present invention;

[0054] Figure 4B A result diagram of the fluorescence quantitative analysis of the total amount of protein molecules adsorbed by the antifouling developing coating material of the present invention;

[0055] FIG5 is a graph showing the results of the antibacterial adhesion test of the antifouling developing coating material of the present invention; A is a photograph showing the results of the antibacterial adhesion test; and B is a graph showing the results of the quantitative analysis of the adsorbed bacterial colonies;

[0056] FIG6 is a graph showing the results of an anti-platelet adhesion test of the anti-fouling developing coating material of the present invention; A is a photograph showing the results of the anti-platelet adhesion test; and B is a graph showing the results of a quantitative analysis of the number of adhered platelets;

[0057] FIG. 7 is an X-ray development diagram of the antifouling developing coating material of the present invention after coating the substrate; A is an X-ray development photograph of different development methods; and B is a normalized development intensity analysis diagram. DETAILED DESCRIPTION

[0058] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0059] Example 1

[0060] This embodiment provides an anti-fouling developing coating material, which is prepared by a method comprising the following steps:

[0061]

[0062] 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 methacryloyloxypropyl tris(trimethylsiloxy)silane 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 ether for precipitation, and the modified phosphorylcholine polymer was obtained by filtration and drying. The reaction is shown below. The NMR result of the polymer is as follows: Figure 1 shown.

[0063] 2) Dissolve barium chloride in double distilled water to 200 mg / ml, and then mix it with 600 mg / ml modified phosphorylcholine polymer in a methanol / water binary solvent to a total concentration of 400 mg / ml. Stir thoroughly at room temperature for 6 hours to allow the barium ions to combine with the sulfonic acid groups of the modified phosphorylcholine polymer, thereby forming an antifouling developing polymer that can be coated on any silicon-based substrate, i.e., an antifouling developing coating material. The molecular structure of the antifouling developing coating material is as follows:

[0064]

[0065] Among them, m=20, n=10, k=3.

[0066] Example 2

[0067] 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 ether for precipitation, and filtered and dried to obtain a modified phosphorylcholine polymer. The NMR results of the polymer were compared with those of the polymer in Example 1. Figure 2 shown.

[0068] 2) Dissolve barium chloride in double distilled water to 200 mg / ml, and then mix it with 600 mg / ml modified phosphorylcholine polymer in a methanol / water binary solvent to a total concentration of 400 mg / ml. Stir thoroughly at room temperature for 6 hours to allow the barium ions to combine with the sulfonic acid groups of the modified phosphorylcholine polymer to form an antifouling developing polymer that can be coated on any silicon-based substrate, i.e., an antifouling developing coating material. The molecular structure of the antifouling developing coating material is as follows:

[0069]

[0070] Among them, m=20, n=10, k=3.

[0071] Example 3

[0072] The antifouling developing coating material of Example 1 was used to coat the antifouling developing coating on a glass sheet, a silicone sheet, a polyurethane sheet and a stainless steel syringe needle tip, and the morphology was observed using a scanning electron microscope (S-3400N). The results are as follows: Figure 3As shown, A is a scanning electron microscope photo coated on a glass sheet, B is a scanning electron microscope photo coated on a silicone sheet, C is a scanning electron microscope photo coated on a polyurethane sheet, and D is a scanning electron microscope photo coated on a stainless steel syringe needle tip. It can be found that the overall surface of the antifouling developer polymer coating part is smooth, with a clear boundary with the uncoated part, and the coated part has no obvious defects or cracks, showing the stability of the antifouling developer material of the present invention when coated on different substrates.

[0073] Example 4

[0074] The anti-fouling developing coating material of Example 1 was used to conduct 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 pre-labeled with fluorescence and the adsorption experiment was carried out for 21 days. On the 3rd, 14th and 21st days, the adsorption of various molecules on the coating was observed using a fluorescence microscope (Nikon Eclipse TE / Ti). The control group was a blank control without the anti-fouling developing coating. The results are shown in Figure 2. Figure 4A and Figure 4B (In the figure, the 3rd, 14th and 21st days are marked as day3, day14 and day21 respectively, uncoating means uncoated, and coating means coated).

[0075] like Figure 4A As shown in the figure, the coating exhibits excellent anti-protein adsorption ability compared with the blank control. Serum protein is hardly adsorbed on the coating, and the amount of fibrin adsorbed on the anti-fouling developing coating is also very small, while the blank control group is full of protein molecules adsorbed on it. Furthermore, the total amount of adsorbed molecules was quantitatively analyzed by fluorescence, as shown in Figure 2. Figure 4B As shown, compared with the blank control group, the total amount of protein adsorbed on the anti-fouling developing coating was significantly reduced, demonstrating the extremely strong anti-protein adsorption ability of the anti-fouling developing coating.

[0076] Example 5

[0077] The anti-fouling developer coating material of Example 1 was used to conduct an anti-bacterial adhesion test. In terms of anti-bacterial adhesion, the anti-bacterial adsorption ability of the anti-fouling developer coating was characterized and tested using Candida albicans (C.albicans), Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus). The sample was soaked in three kinds of live bacteria solution with high concentration (108 / mL), and the live bacteria were replaced every three days. After soaking for 2 weeks, it was taken out and dried, and the number of bacteria on it was observed using a scanning electron microscope (SEM). The solvent was dialysate to ensure bacterial activity, and the control group was a blank control. The results are as follows Figure 5A and Figure 5B shown.

[0078] like Figure 5A As shown in the figure, under the adsorption of three different bacteria, after 2 weeks, there were obvious large colonies on the control group without antifouling developing coating, while no obvious colony growth was observed on the sample coated with antifouling developing coating. Further, the adsorbed colonies were quantitatively analyzed, and the results are shown in Figure 5B As shown, the samples using the antifouling developer coating showed a significant reduction in bacterial adhesion, with the amount of bacterial adhesion reduced by 95% after 2 weeks.

[0079] Example 6

[0080] The anti-fouling developing coating material of Example 1 was used to conduct an anti-platelet adhesion test. The anti-fouling developing coating was coated on different substrate materials such as NiTi, PVC and TPU, and the platelets were contacted with the test materials, 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 FIG. Fig. 6A and Figure 6B As shown. Fig. 6A As shown in Figure 2, the antifouling developing coating exhibited significant anti-platelet adhesion effects on all three materials. The quantitative analysis of the number of adhered platelets showed that Figure 6B As shown, it can be seen that the anti-platelet adhesion effect is significantly enhanced with the increase of coating concentration.

[0081] Example 7

[0082] The antifouling developing coating material of Example 1 was used to perform an X-ray development test. The barium sulfate solution and the antifouling developing coating material of the present invention were coated on a rectangular glass substrate, respectively, 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 FIG. Fig. 7A and Figure 7B As shown, Fig. 7A It is X-ray development photos of different development methods; Figure 7B It is a normalized development intensity analysis diagram; it can be seen that the development effect of the anti-fouling development coating material of the present invention is similar to that of barium sulfate, although slightly lower than that of the commercial platinum iridium development ring, but much higher than that of the blank control group. It can be seen that the anti-fouling development coating material of the present invention has an X-ray development effect comparable to that of barium sulfate.

[0083] It can be seen from the above that the antifouling and developing coating material of the present invention has excellent coating performance, antifouling performance and X-ray developing effect.

[0084] The modified phosphorylcholine polymer part in the antifouling developing coating material of the present invention serves as an antifouling unit, and the bound barium serves as a developing unit, and the antifouling and developing properties are excellent. The siloxane group in the antifouling unit can form a covalent bond with the surface of the substrate so that the coating is firmly bonded to the substrate, ensuring the bonding stability and safety of the antifouling developing coating material of the present invention on the substrate. For example, the siloxane group can be covalently bonded to the silicon-based substrate material, has excellent stability, will not be lost or fall off over time, and significantly improves the durability and reliability of the developing coating; the siloxane group can also be bonded to other substrate surfaces through hydrophobic effects and van der Waals forces, thereby providing flexibility and applicability for the wide application of the developing coating. The antifouling developing coating material of the present invention can be coated on the surfaces of various substrates, including silicon-based substrates (such as glass substrates), metal substrates, and various plastic and high molecular polymer substrates (such as silicone rubber, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, etc.), and has wide applicability; the application fields are wide, for example, it can be used in the fields of medical devices, optical lenses and industrial printing. The coating gives the coated object the dual functions of antifouling and X-ray imaging, and exhibits excellent X-ray absorption performance during development, especially can provide accurate and clear development effects for medical imaging, and provide reliable imaging information for medical imaging.

[0085] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the anti-fouling developing coating material and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An antifouling developing coating material, characterized in that: The anti-fouling developing coating material has a structure as shown in the following formula I: Wherein m=1-40, n=1-40, k=1-5, R1 and R2 are siloxane-containing groups, and R1 and R2 are the same or different.

2. The antifouling developing coating material according to claim 1, characterized in that: m:n=1:1~4:

1.

3. The antifouling developing coating material according to claim 1 or 2, characterized in that: R1 and R2 are independently selected from tris(trimethylsiloxy)silyl or trimethoxysilyl, and the structure thereof is as follows:

4. The method for preparing an antifouling developing coating material according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: (1) preparing a modified phosphorylcholine polymer modified with siloxane and sulfonate; (2) adding a barium salt to a solution containing the modified phosphorylcholine polymer modified with siloxane and sulfonate to react and obtain the antifouling developing coating material.

5. The preparation method according to claim 4, characterized in that: The step (1) specifically includes the following steps: 2-methacryloyloxyethyl phosphorylcholine reacts with a siloxane compound and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonatepropyl)ammonium hydroxide to obtain the modified phosphorylcholine polymer modified with siloxane and sulfonate.

6. The preparation method according to claim 5, characterized in that: The siloxane compound is methacryloxypropyl tris(trimethylsiloxy)silane, methacryloxypropyl tris(trimethoxy)silane or vinyl trimethoxysilane.

7. The preparation method according to claim 5, characterized in that: The molar ratio of the 2-methacryloyloxyethyl phosphorylcholine to the siloxane compound is 1:1-8:

1.

8. The preparation method according to claim 5, characterized in that: The reaction of 2-methacryloyloxyethyl phosphorylcholine with the siloxane compound is carried out in the presence of 4-cyano-4-(thiobenzoyl)valeric acid.

9. The preparation method according to claim 8, characterized in that: The molar ratio of the 2-methacryloyloxyethyl phosphorylcholine to 4-cyano-4-(thiobenzoyl)pentanoic acid is 1:1-5:

1.

10. The preparation method according to claim 5, characterized in that: The reaction of 2-methacryloyloxyethyl phosphorylcholine and the siloxane compound is carried out in the presence of an initiator.

11. The preparation method according to claim 10, characterized in that: The initiator is selected from azobisisobutyronitrile.

12. The preparation method according to claim 10, characterized in that: The molar ratio of the 2-methacryloyloxyethyl phosphorylcholine to the initiator is 1:1-5:

1.

13. The preparation method according to claim 5, characterized in that: The molar ratio of the 2-methacryloyloxyethyl phosphorylcholine to (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide is 2:1-8:

1.

14. The preparation method according to claim 5, characterized in that: The reaction temperature in step (1) is 60°C-70°C, and the reaction time is 16-64h.

15. The preparation method according to claim 5, characterized in that: 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.

16. The preparation method according to claim 5, characterized in that: The reaction in step (1) is carried out under nitrogen protection.

17. The preparation method according to claim 5, characterized in that: A more specific operation of step (1) is: dissolving 2-methacryloyloxyethyl phosphorylcholine, 4-cyano-4-(thiobenzoyl)valeric acid, and azobisisobutyronitrile in n-propanol, heating to 60°C-70°C under nitrogen protection, stirring and reacting for 16-32 hours, then adding a siloxane compound and (2-(methacryloyloxy)ethyl)dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, and continuing the reaction for 16-32 hours to obtain the modified phosphorylcholine polymer modified with siloxane and sulfonate.

18. The preparation method according to claim 5, characterized in that: 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.

19. The preparation method according to claim 4, characterized in that: The barium salt in step (2) is selected from one of barium chloride, barium sulfate, barium nitrate or barium carbonate, or a mixture of at least two of them.

20. The preparation method according to claim 4, characterized in that: The molar ratio of the modified phosphorylcholine polymer modified with siloxane and sulfonate to the barium salt added in step (2) is in the range of 1:1 to 4:

1.

21. The preparation method according to claim 20, characterized in that: The molar ratio of the modified phosphorylcholine polymer modified with siloxane and sulfonate to the barium salt added in step (2) is 1:

1.

22. The preparation method according to claim 4, characterized in that: The solvent in the solution of step (2) is a mixed solvent of methanol and water.

23. The preparation method according to claim 4, characterized in that: The reaction in step (2) is carried out at room temperature and the reaction time is 6 to 12 hours.

24. Use of the antifouling developing coating material according to any one of claims 1 to 3 in coating a substrate surface.

25. The use according to claim 24, characterized in that The substrate surface includes a silicon-based surface, a glass-based surface, a metal-based surface, and a high-molecular polymer-based surface.

26. An antifouling developing coating, characterized in that: The raw material for preparing the anti-fouling developing coating comprises the anti-fouling developing coating material according to any one of claims 1 to 3.

27. Use of the antifouling developing coating material according to any one of claims 1 to 3 in medical devices or medical materials, optical lenses or industrial printing.

Citation Information

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