A developing coating, its preparation method and application

Abstract

The present application discloses a developing coating, a preparation method thereof, and an application, relating to the technical field of medical imaging. It includes acrylic resin at 45-55% by mass percentage, n-butanol at 15-25%, n-hexane at 8-15%, color paste at 3-5%, fumed silica at 2-4%, barium sulfate at 8-12%, nano tungsten oxide at 3-8%, leveling agent at 1-2%, and wetting agent at 1-2%. Among them, the nano tungsten oxide and the barium sulfate are compounded to form BaSO4@X / WO3 particles. The present application obtains a developing coating through preparation, achieving the effects of perfect fitting with the patient's skin, clear developing pattern, convenient use, reduced error and surgical wound. While improving the surgical efficiency, it effectively reduces the operation damage during the operation, and at the same time solves the problem of developing blind areas or inconsistent contrast caused by excessive concentration of barium sulfate and nano tungsten oxide locally.

Description

Technical Field

[0001] This application relates to the field of medical imaging technology, and particularly relates to a developing coating, a preparation method thereof, and an application. Background Art

[0002] A developing coating is a material with special functions and has important applications in the orthopedic field. Currently, the main components of orthopedic developing coatings include a polymer matrix, a developer, and other additives. The polymer matrix is usually a material with good biocompatibility, such as polymethyl methacrylate (PMMA), etc., which provides adhesion and mechanical properties for the coating. The developer is the key component, and commonly used ones include barium sulfate, tantalum oxide, etc. These substances can absorb or scatter rays during imaging examinations, thus forming an obvious contrast on the image.

[0003] Chinese Patent with Publication No. CN115645605B discloses a developing bone cement, a preparation method thereof, and uses. The developing bone cement is composed of a powder containing a developer and a liquid. The developer includes insoluble tungsten compounds. The tungsten compounds are barium tungstate (BaWO4), strontium tungstate (SrWO4), calcium tungstate (CaWO4), cobalt tungstate (CoWO4), cadmium tungstate (CdWO4), ferrous tungstate (FeWO4), and tungsten-containing ceramics including tungsten carbide (WC), tungsten oxide (WO3), tungsten boride (WB2), etc.; and the insoluble tungsten compounds are one or more of tungsten carbide, tungsten oxide, and tungsten boride.

[0004] However, although the mass ratio of the tungsten-containing developer in the developing bone cement, its preparation method, and uses is reduced to 10% and a good developing effect is achieved, it still has the problem of toxicity caused by contact with the human body. Moreover, during the addition process of the developer, its dispersibility and stability among the components are also insufficient, which also affects the imaging effect and diagnostic accuracy and needs to be improved. Summary of the Invention

[0005] In view of this, the first object of this application is to provide a developing coating to achieve the purpose of improving the developing effect and strong adhesion. The specific scheme is as follows:

[0006] A developing coating, comprising 45 - 55% by mass of acrylic resin, 15 - 25% of n-butanol, 8 - 15% of n-hexane, 3 - 5% of color paste, 2 - 4% of fumed silica, 8 - 12% of barium sulfate, 3 - 8% of nano tungsten oxide, 1 - 2% of leveling agent, and 1 - 2% of wetting agent;

[0007] Among them, the nano tungsten oxide and the barium sulfate are compounded to form BaSO4@X / WO3 particles, and the nano tungsten oxide is ICG-modified nano rod-shaped tungsten oxide, and the ICG-modified nano rod-shaped tungsten oxide is obtained by loading ICG.

[0008] Preferably, the leveling agent is a fluorine-modified acrylic leveling agent, a natural oil leveling agent or a silicone leveling agent.

[0009] Preferably, the wetting agent is a polyether wetting agent, a sugar derivative wetting agent or a siloxane wetting agent.

[0010] Preferably, the preparation of the BaSO4@X / WO3 particles includes the following steps: Step ①: Obtain a dispersion solvent in a water or ethanol solution containing 1-3 wt% PVP; Step ②: Put the ICG-modified nano rod-shaped tungsten oxide into the dispersion solvent for dispersion to obtain a tungsten oxide suspension containing 1-5 wt%, and put the barium sulfate into the dispersion solvent for dispersion to obtain a barium sulfate suspension containing 10-30 wt%; Step ③: Drop the tungsten oxide suspension into the stirred barium sulfate suspension, and continue to stir for 1-2 h after the dropping is completed to obtain a stirred composite liquid; Step ④: Let the stirred composite liquid stand for aging for 12-24 h, and then obtain the finished BaSO4@X / WO3 particles after centrifugation, washing with deionized water and drying in sequence.

[0011] The second object of the present application is to provide a preparation method of a developing coating, including the following steps:

[0012] Step 1: Prepare materials: Prepare acrylic resin, n-butanol, n-hexane, color paste, fumed silica, barium sulfate, nano tungsten oxide, leveling agent and wetting agent according to the corresponding mass percentages for standby;

[0013] Step 2: Modification treatment: Subject the barium sulfate to surface activation treatment to obtain activated barium sulfate, obtain ICG-modified nano rod-shaped tungsten oxide by loading ICG on the nano tungsten oxide, and then compound the activated barium sulfate with the ICG-modified nano rod-shaped tungsten oxide to form BaSO4@X / WO3 particles for standby;

[0014] Step 3: Mix for standby: Mix the acrylic resin, n-butanol, n-hexane, color paste, fumed silica, leveling agent and wetting agent evenly, add the BaSO4@X / WO3 particles and continue to stir and mix evenly to obtain the finished developing coating for standby.

[0015] Preferably, the barium sulfate is surface-activated barium sulfate, and the surface activation treatment is silane coupling agent modification treatment, carboxylation treatment, surfactant modification treatment or mixing with barium chloride in a mass ratio of 1:0.02-0.1 followed by precipitation treatment.

[0016] Preferably: the silane coupling agent is γ-aminopropyltriethoxysilane, and the modification treatment of the silane coupling agent includes putting γ-aminopropyltriethoxysilane and barium sulfate into ethanol, methanol or DMF, and stirring at 40-80 °C for 2-4 h to obtain surface-activated barium sulfate; the carboxylation treatment includes putting succinic anhydride and barium sulfate into DMSO, and stirring at 60-80 °C for 6-12 h to obtain activated barium sulfate; the precipitation treatment includes mixing barium sulfate and barium chloride in a mass ratio of 1:0.02-0.1 in deionized water, and then stirring and reacting at 50-70 °C to obtain surface-activated barium sulfate, and the concentrations of barium sulfate and barium chloride are 0.1-0.5 mol / L; the surface activation treatment also includes centrifugation, washing and precipitation, and dry barium sulfate is obtained.

[0017] Preferably: the preparation of the ICG-modified nanorod tungsten oxide includes step ① putting nanorod tungsten oxide into DMSO for dispersion to obtain a tungsten oxide suspension containing 1-2 wt%, and putting ICG into ethanol to obtain a 1-10 wt% ICG solution; step ② mixing the tungsten oxide suspension and the ICG solution and stirring to obtain a preliminarily mixed material; step ③ subjecting the preliminarily mixed material to ultrasonic treatment, controlling the ultrasonic treatment time to be 1-2 h and the power to be 100-300 W to obtain ICG-modified nanorod tungsten oxide.

[0018] The third object of the present application is to provide an application of a developing coating, including using the developing coating as described above and applying it to the production of a medical orthopedic developing surgical positioning film.

[0019] Preferably: the medical orthopedic developing surgical positioning film includes a medical adhesive, a permeable mesh and a polymer developing film layer; the polymer developing film layer is formed by coating and photo / thermal curing of the developing coating.

[0020] As can be seen from the above solution, the present application provides a developing coating, a preparation method thereof, and an application. The preparation method of the developing coating has the effect of obtaining a developing coating with effectively improved developing effect and strong adhesion, and the application of the developing coating has the effects of perfectly fitting with the patient's skin, clear developing pattern, convenient use, reduced error and surgical wound, thereby significantly improving the surgical efficiency while effectively avoiding unnecessary harm to the patient during the operation. The developing coating can effectively avoid the problem that barium sulfate blocks the absorption and scattering of near-infrared light by tungsten oxide nanorods or tungsten oxide nanorods block barium sulfate, and further causes a developing blind area or inconsistent contrast due to the excessive concentration of barium sulfate and tungsten oxide nanorods in a local area. At the same time, the BaSO4@X / WO3 particles formed by compounding barium sulfate and tungsten oxide nanorods have the effect of loading barium sulfate on the nanorod structure of tungsten oxide nanorods, and further promoting the developing performance of the developing coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only the embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained according to the provided drawings.

[0022] Figure 1 It is a schematic structural diagram of a medical orthopedic developing surgical positioning film disclosed in the present application.

[0023] Description of the reference numerals: 1, polymer developing film layer; 2, permeable mesh; 3, medical adhesive. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0024] The following will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments of the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present application.

[0025] It should be mentioned that directly optimizing and reducing the particle size of tungsten oxide nanorods to achieve the developing performance and the dispersion performance of tungsten oxide nanorods in the developing coating is obviously a conventional implementation method. However, when the particle size of tungsten oxide nanorods is small enough, it will significantly affect the preparation cost of the developing coating, and when the particle size continues to decrease, it is difficult to substantially improve the developing performance. Therefore, in the embodiments of the present application, the particle size distribution of barium sulfate is controlled to be 0.5 - 1 μm, and the particle size distribution of tungsten oxide nanorods is 50 - 100 nm.

[0026] Meanwhile, in this application, the leveling agent can be a fluorine-modified acrylic leveling agent, a natural oil leveling agent, or a silicone leveling agent. The wetting agent can be a polyether wetting agent, a sugar derivative wetting agent, or a siloxane wetting agent. Details are not elaborated here. Of course, the leveling agent in the embodiment of this application is BYK-333 purchased from BYK, and the wetting agent is TEGO270 purchased from Degussa.

[0027] The following will specifically describe the developing coating, its preparation method, and application of this application.

[0028] A developing coating includes 45-55% acrylic resin, 15-25% n-butanol, 8-15% n-hexane, 3-5% color paste, 2-4% fumed silica, 8-12% barium sulfate, 3-8% nanometer tungsten oxide, 1-2% leveling agent, and 1-2% wetting agent by mass percentage. Among them, nanometer tungsten oxide and barium sulfate are compounded to form BaSO4@X / WO3 particles. Meanwhile, the nanometer tungsten oxide is ICG-modified nanorod-shaped tungsten oxide, and the ICG-modified nanorod-shaped tungsten oxide is obtained by ICG loading.

[0029] It should be noted that the preparation of BaSO4@X / WO3 particles includes the following steps: Step ①, obtaining a dispersion solvent in an aqueous or ethanol solution containing 1-3 wt% PVP; Step ②, putting the ICG-modified nanorod-shaped tungsten oxide into the dispersion solvent for dispersion to obtain a tungsten oxide suspension containing 1-5 wt%, and putting barium sulfate into the dispersion solvent for dispersion to obtain a barium sulfate suspension containing 10-30 wt%; Step ③, dropping the tungsten oxide suspension into the stirred barium sulfate suspension, and continuing to stir for 1-2 h after the dropping is completed to obtain a stirred composite liquid; Step ④, subjecting the stirred composite liquid to static aging treatment for 12-24 h, and then obtaining the finished BaSO4@X / WO3 particles through centrifugation, deionized water washing, and drying in sequence.

[0030] A preparation method of a developing coating includes the following steps:

[0031] Step 1, preparing materials: preparing acrylic resin, n-butanol, n-hexane, color paste, fumed silica, barium sulfate, nanometer tungsten oxide, leveling agent, and wetting agent according to the corresponding mass percentages for standby;

[0032] Step 2, modification treatment: subjecting barium sulfate to surface activation treatment to obtain activated barium sulfate, obtaining ICG-modified nanorod-shaped tungsten oxide by ICG loading of nanometer tungsten oxide, and then compounding the activated barium sulfate with the ICG-modified nanorod-shaped tungsten oxide to form BaSO4@X / WO3 particles for standby;

[0033] Step 3. Mix for standby: After uniformly mixing acrylic resin, n-butanol, n-hexane, color paste, fumed silica, flow agent and wetting agent, add BaSO4@X / WO3 particles and continue to stir and mix evenly to obtain the finished developing coating for standby.

[0034] Among them, the barium sulfate is surface-activated barium sulfate. The surface activation treatment is silane coupling agent modification treatment, carboxylation treatment, surfactant modification treatment or mixing with barium chloride in a mass ratio of 1:0.02 - 0.1 and then performing precipitation treatment.

[0035] It should be noted that the silane coupling agent is γ-aminopropyltriethoxysilane, and the silane coupling agent modification treatment includes putting γ-aminopropyltriethoxysilane and barium sulfate into ethanol, methanol or DMF, and stirring at 40 - 80 °C for 2 - 4 h to obtain surface-activated barium sulfate. The carboxylation treatment includes putting succinic anhydride and barium sulfate into DMSO, and stirring at 60 - 80 °C for 6 - 12 h to obtain activated barium sulfate. The precipitation treatment includes mixing barium sulfate and barium chloride in a mass ratio of 1:0.02 - 0.1 in deionized water, and then stirring and reacting at 50 - 70 °C to obtain surface-activated barium sulfate, and the concentration of the barium sulfate and barium chloride is 0.1 - 0.5 mol / L; the surface activation treatment also includes centrifugation, washing and precipitation, and obtaining dried barium sulfate. Of course, in the embodiments of the present application, the silane coupling agent modification treatment is mainly adopted, and details are not described here.

[0036] In the embodiments of the present application, the preparation of ICG-modified nanorod tungsten oxide includes Step ① putting nanorod tungsten oxide into DMSO for dispersion to obtain a tungsten oxide suspension containing 1 - 2 wt%, and putting ICG into ethanol to obtain a 1 - 10 wt% ICG solution; Step ② mixing the tungsten oxide suspension and the ICG solution and stirring to obtain a preliminary mixed material; Step ③ performing ultrasonic treatment on the preliminary mixed material, controlling the ultrasonic treatment time to be 1 - 2 h and the power to be 100 - 300 W to obtain ICG-modified nanorod tungsten oxide.

[0037] An application of a developing coating, including using the developing coating as described above and applying it to the production of a medical orthopedic imaging surgery positioning film. As Figure 1 shown, the medical orthopedic imaging surgery positioning film includes a medical adhesive, a permeable mesh and a polymer imaging film layer, and the polymer imaging film layer is formed by coating and photo / thermal curing of the developing coating.

[0038] Example 1

[0039] A developing coating, comprising 45% acrylic resin, 15% n-butanol, 15% n-hexane, 5% color paste, 2% fumed silica, 10% barium sulfate, 5% nanometer tungsten oxide, 2% leveling agent and 1% wetting agent by mass percentage. Among them, the nanometer tungsten oxide and barium sulfate are compounded to form BaSO4@X / WO3 particles. At the same time, the nanometer tungsten oxide is ICG-modified nanorod-shaped tungsten oxide, and the ICG-modified nanorod-shaped tungsten oxide is obtained by ICG loading.

[0040] It should be noted that the preparation of BaSO4@X / WO3 particles includes the following steps: Step ①, obtaining a dispersion solvent in a water or ethanol solution containing 1 wt% PVP; Step ②, putting the ICG-modified nanorod-shaped tungsten oxide into the dispersion solvent for dispersion to obtain a tungsten oxide suspension containing 1 wt%, and putting barium sulfate into the dispersion solvent for dispersion to obtain a barium sulfate suspension containing 10 wt%; Step ③, dropping the tungsten oxide suspension into the stirred barium sulfate suspension, and continuing to stir for 1 h after the dropping is completed to obtain a stirred composite liquid; Step ④, standing and aging the stirred composite liquid for 12 h, and then successively centrifuging, washing with deionized water and drying to obtain the finished BaSO4@X / WO3 particles.

[0041] A preparation method of a developing coating, comprising the following steps:

[0042] Step 1, preparing materials: preparing acrylic resin, n-butanol, n-hexane, color paste, fumed silica, barium sulfate, nanometer tungsten oxide, leveling agent and wetting agent according to the corresponding mass percentages for standby;

[0043] Step 2, modification treatment: subjecting barium sulfate to surface activation treatment to obtain activated barium sulfate, obtaining ICG-modified nanorod-shaped tungsten oxide by ICG loading of nanometer tungsten oxide, and then compounding the activated barium sulfate and the ICG-modified nanorod-shaped tungsten oxide to form BaSO4@X / WO3 particles for standby;

[0044] Step 3, mixing for standby: mixing acrylic resin, n-butanol, n-hexane, color paste, fumed silica, leveling agent and wetting agent evenly, adding BaSO4@X / WO3 particles and continuing to stir and mix evenly to obtain the finished developing coating for standby.

[0045] Among them, the barium sulfate is surface-activated barium sulfate. The surface activation treatment is silane coupling agent modification treatment, carboxylation treatment, surfactant modification treatment or mixing with barium chloride in a mass ratio of 1:0.02 - 0.1 and then treating by precipitation method.

[0046] It should be noted that the silane coupling agent is γ-aminopropyltriethoxysilane, and the modification treatment of the silane coupling agent includes putting γ-aminopropyltriethoxysilane and barium sulfate into ethanol, methanol or DMF, and stirring at 40 °C for 2 h to obtain surface-activated barium sulfate.

[0047] In the embodiment of the present application, the preparation of ICG-modified nanorod tungsten oxide includes step ① putting nanorod tungsten oxide into DMSO for dispersion to obtain a tungsten oxide suspension containing 1 wt%, and putting ICG into ethanol to obtain a 1 wt% ICG solution; step ② mixing the tungsten oxide suspension and the ICG solution and stirring to obtain a preliminary mixture; step ③ subjecting the preliminary mixture to ultrasonic treatment, controlling the ultrasonic treatment time to be 1 h and the power to be 300 W to obtain ICG-modified nanorod tungsten oxide.

[0048] An application of a developing coating, including using the developing coating as described above and applying it to the production of a medical orthopedic developing surgical positioning film. As Figure 1 shown, the medical orthopedic developing surgical positioning film includes a medical adhesive, a permeable mesh and a polymer developing film layer, and the polymer developing film layer is formed by coating and photo / thermal curing of the developing coating.

[0049] Example Two

[0050] A developing coating includes 55% acrylic resin, 17% n-butanol, 8% n-hexane, 3% color paste, 2.8% fumed silica, 8% barium sulfate, 3% nano tungsten oxide, 2% leveling agent and 1.2% wetting agent by mass percentage. Among them, nano tungsten oxide and barium sulfate are compounded to form BaSO4@X / WO3 particles. At the same time, the nano tungsten oxide is ICG-modified nanorod tungsten oxide, and the ICG-modified nanorod tungsten oxide is obtained by ICG loading.

[0051] It should be noted that the preparation of BaSO4@X / WO3 particles includes step ① obtaining a dispersion solvent in a water or ethanol solution containing 1-3 wt% PVP; step ② putting ICG-modified nanorod tungsten oxide into the dispersion solvent for dispersion to obtain a tungsten oxide suspension containing 3 wt%, and putting barium sulfate into the dispersion solvent for dispersion to obtain a barium sulfate suspension containing 20 wt%; step ③ dropping the tungsten oxide suspension into the stirred barium sulfate suspension, and continuing to stir for 1.5 h after the dropping is completed to obtain a stirred composite liquid; step ④ subjecting the stirred composite liquid to static aging treatment for 18 h, and then successively centrifuging, washing with deionized water and drying to obtain the finished BaSO4@X / WO3 particles.

[0052] A preparation method of a developing coating includes the following steps:

[0053] Step 1, Prepare materials: Prepare acrylic resin, n-butanol, n-hexane, color paste, fumed silica, barium sulfate, nano tungsten oxide, leveling agent and wetting agent according to the corresponding mass percentages for standby;

[0054] Step 2, Modification treatment: Subject barium sulfate to surface activation treatment to obtain activated barium sulfate, and subject nano tungsten oxide to ICG loading to obtain ICG-modified nanorod tungsten oxide. Then, compound the activated barium sulfate with the ICG-modified nanorod tungsten oxide to form BaSO4@X / WO3 particles for standby;

[0055] Step 3, Mix for standby: After mixing acrylic resin, n-butanol, n-hexane, color paste, fumed silica, leveling agent and wetting agent evenly, add BaSO4@X / WO3 particles and continue to stir and mix evenly to obtain the ready-developing coating for the finished product for standby.

[0056] Among them, the barium sulfate is surface-activated barium sulfate. The surface activation treatment is silane coupling agent modification treatment, carboxylation treatment, surfactant modification treatment or mixing with barium chloride in a mass ratio of 1:0.02 - 0.1 and then subjecting to precipitation treatment.

[0057] It should be noted that the silane coupling agent is γ-aminopropyltriethoxysilane, and the silane coupling agent modification treatment includes putting γ-aminopropyltriethoxysilane and barium sulfate into ethanol, methanol or DMF and subjecting to stirring treatment at 80°C for 2h to obtain the surface-activated barium sulfate.

[0058] In the embodiment of the present application, the preparation of the ICG-modified nanorod tungsten oxide includes Step ① putting the nanorod tungsten oxide into DMSO for dispersion to obtain a tungsten oxide suspension containing 1 - 2wt%, and putting ICG into ethanol to obtain a 5wt% ICG solution; Step ② mixing the tungsten oxide suspension and the ICG solution and subjecting to stirring treatment to obtain a preliminary mixed material; Step ③ subjecting the preliminary mixed material to ultrasonic treatment, controlling the ultrasonic treatment time to be 1.5h and the power to be 200W to obtain the ICG-modified nanorod tungsten oxide.

[0059] An application of a developing coating, including using the developing coating as described above and applying it to the production of a medical orthopedic imaging surgical positioning film. As Figure 1 shown, the medical orthopedic imaging surgical positioning film includes a medical adhesive, a permeable mesh and a polymer imaging film layer, and the polymer imaging film layer is formed by coating the developing coating and subjecting to light / heat curing.

[0060] Example Three

[0061] A developing coating material includes acrylic resin at 46% by mass percentage, n-butanol at 18%, n-hexane at 9%, color paste at 4%, fumed silica at 2%, barium sulfate at 10%, nano tungsten oxide at 8%, leveling agent at 2%, and wetting agent at 1%. Among them, nano tungsten oxide and barium sulfate are compounded to form BaSO4@X / WO3 particles. At the same time, the nano tungsten oxide is ICG-modified nano rod-shaped tungsten oxide, and the ICG-modified nano rod-shaped tungsten oxide is obtained by ICG loading.

[0062] It should be noted that the preparation of BaSO4@X / WO3 particles includes the following steps: Step ①, obtain a dispersion solvent in an aqueous or ethanol solution containing 3 wt% PVP; Step ②, put the ICG-modified nano rod-shaped tungsten oxide into the dispersion solvent for dispersion to obtain a tungsten oxide suspension containing 5 wt%, and put barium sulfate into the dispersion solvent for dispersion to obtain a barium sulfate suspension containing 30 wt%; Step ③, drop the tungsten oxide suspension into the stirred barium sulfate suspension, and continue stirring for 2 h after the dropping is completed to obtain a stirred composite liquid; Step ④, let the stirred composite liquid stand for aging treatment for 24 h, and then obtain the finished BaSO4@X / WO3 particles after centrifugation, washing with deionized water, and drying in sequence.

[0063] A preparation method of a developing coating material includes the following steps:

[0064] Step 1, prepare materials: Prepare acrylic resin, n-butanol, n-hexane, color paste, fumed silica, barium sulfate, nano tungsten oxide, leveling agent, and wetting agent according to the corresponding mass percentages for standby;

[0065] Step 2, modification treatment: Subject barium sulfate to surface activation treatment to obtain activated barium sulfate, obtain ICG-modified nano rod-shaped tungsten oxide by ICG loading of nano tungsten oxide, and then compound the activated barium sulfate with the ICG-modified nano rod-shaped tungsten oxide to form BaSO4@X / WO3 particles for standby;

[0066] Step 3, mix for standby: Mix acrylic resin, n-butanol, n-hexane, color paste, fumed silica, leveling agent, and wetting agent evenly, add BaSO4@X / WO3 particles, and continue stirring and mixing evenly to obtain the finished developing coating material for standby.

[0067] Among them, the barium sulfate is surface-activated barium sulfate. The surface activation treatment is silane coupling agent modification treatment, carboxylation treatment, surfactant modification treatment, or mixing with barium chloride in a mass ratio of 1:0.1 and then subjecting to precipitation treatment.

[0068] It should be noted that the silane coupling agent is γ-aminopropyltriethoxysilane, and the modification treatment of the silane coupling agent includes putting γ-aminopropyltriethoxysilane and barium sulfate into DMF, and stirring at 60 °C for 3 h to obtain surface-activated barium sulfate.

[0069] In the embodiment of the present application, the preparation of ICG-modified nanorod tungsten oxide includes step ① putting nanorod tungsten oxide into DMSO for dispersion to obtain a tungsten oxide suspension containing 2 wt%, and putting ICG into ethanol to obtain a 10 wt% ICG solution; step ② mixing the tungsten oxide suspension and the ICG solution and stirring to obtain a preliminary mixed material; step ③ subjecting the preliminary mixed material to ultrasonic treatment, controlling the ultrasonic treatment time to be 2 h and the power to be 100 W to obtain ICG-modified nanorod tungsten oxide.

[0070] An application of a developing coating, including using the developing coating as described above and applying it to the production of a medical orthopedic developing surgical positioning film. As Figure 1 shown, the medical orthopedic developing surgical positioning film includes a medical adhesive, a permeable mesh, and a polymer developing film layer, and the polymer developing film layer is formed by coating the developing coating and curing it by light / heat.

[0071] Comparative Example 1

[0072] The difference between Comparative Example 1 and Example 2 is that the nano tungsten oxide in Comparative Example 1 is nanorod tungsten oxide without ICG loading.

[0073] Comparative Example 2

[0074] The difference between Comparative Example 2 and Example 2 is that the barium sulfate in Comparative Example 2 is not surface-activated.

[0075] Comparative Example 3

[0076] The difference between Comparative Example 3 and Example 2 is that the barium sulfate and nano tungsten oxide in Comparative Example 3 are directly mixed with the other components without forming BaSO4@X / WO3 particles by compounding.

[0077] Comparative Example 4

[0078] The difference between Comparative Example 4 and Example 2 is that the nano tungsten oxide in Comparative Example 4 is nanorod tungsten oxide without ICG loading, and the barium sulfate is not surface-activated. And the barium sulfate and nano tungsten oxide are directly mixed with the other components without forming BaSO4@X / WO3 particles by compounding.

[0079] It should be mentioned that for the above Examples 1 to 3 and Comparative Examples 1 to 3, the imaging performance was tested, and the test method is as follows:

[0080] First, control the tube voltage of the X-ray to be 40 kV, 50 kV, and 60 kV respectively for testing.

[0081] Secondly, control the average thickness of the polymer developing film layer to be 30 - 35 μm, and the actual thickness in the embodiments of the present application is 31.6 ± 0.4 μm.

[0082] Evaluate the development effect for the performance test results of the above-mentioned embodiments and comparative examples, and represent them with I, II, III, IV, and V respectively.

[0083] Among them, I represents excellent development, II represents good development and no development blind area, III represents general development, IV represents general development and local development blind area, and V represents poor development and local development blind area. The test results are shown in Table 1 below.

[0084] Table 1 Performance test results of the medical orthopedic imaging surgery positioning film

[0085]

[0086] As can be seen from Table 1 above, the BaSO4@X / WO3 particles obtained by the preparation and composite preparation of barium sulfate and nano tungsten oxide in the embodiments of the present application have significantly improved the imaging performance of the obtained imaging coating in the application of the polymer imaging film layer, and effectively avoid the problems of imaging blind areas or inconsistent contrast caused by the excessive concentration of barium sulfate and nano tungsten oxide. At the same time, since ICG has the function of further promoting imaging, when it is carried on nano tungsten oxide, it will effectively improve the imaging ability of nano tungsten oxide and promote the composite ability with surface-treated barium sulfate. When the surface of barium sulfate is not treated with activity, it will be difficult to achieve a stable and uniformly dispersed surface between barium sulfate and ICG-modified nanorod-shaped tungsten oxide, thus affecting the distribution effect of the obtained BaSO4@X / WO3 particles in the imaging coating, and further leading to the problem that barium sulfate and nano tungsten oxide block each other and affect the imaging effect.

[0087] In summary, the present application provides a developing coating, a preparation method thereof, and an application. The preparation method of the developing coating has the effect of obtaining a developing coating with effectively improved developing effect and strong adhesion, and the application of the developing coating has the effects of perfect fitting with the patient's skin, clear developing pattern, convenient use, reducing errors and surgical wounds, thereby significantly improving the surgical efficiency while effectively avoiding unnecessary injuries to the patient during the operation. The developing coating can effectively avoid the problem that barium sulfate blocks the absorption and scattering of near-infrared light by tungsten oxide nanorods or tungsten oxide nanorods block the absorption and scattering of near-infrared light by barium sulfate, and further cause the formation of a developing blind area or inconsistent contrast due to the excessive concentration of barium sulfate and tungsten oxide nanorods in a local area. At the same time, the BaSO4@X / WO3 particles formed by compounding barium sulfate and tungsten oxide nanorods have the effect of carrying barium sulfate on the nanorod structure of tungsten oxide nanorods, and further promoting the developing performance of the developing coating.

[0088] The "first", "second", "third", "fourth", etc. (if any) involved in the present application are used to distinguish similar objects and do not necessarily need to describe a specific order or sequence. It should be understood that such data can be interchanged under appropriate circumstances so that the embodiments described herein can be implemented in an order other than that illustrated or described herein. In addition, the terms "comprising" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, or device comprising a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, or devices.

[0089] It should be noted that the descriptions involving "first", "second", etc. in the present application are only for descriptive purposes and should not be construed as indicating or implying their relative importance or implicitly indicating the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions between various embodiments can be combined with each other, but it must be based on the fact that those skilled in the art can implement it. When the combination of technical solutions conflicts or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection required by the present application.

[0090] Specific examples are used in this article to elaborate on the principles and implementation manners of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those of ordinary skill in the art, according to the idea of the present application, there will be changes in the specific implementation manners and application scopes. In summary, the content of this specification should not be construed as a limitation on the present application.

Claims

1. A developing coating, characterized in that: It includes acrylic resin at 45 - 55% by mass percentage, n-butanol at 15 - 25%, n-hexane at 8 - 15%, color paste at 3 - 5%, fumed silica at 2 - 4%, barium sulfate at 8 - 12%, nano tungsten oxide at 3 - 8%, leveling agent at 1 - 2% and wetting agent at 1 - 2%. Among them, the nano tungsten oxide and the barium sulfate are compounded to form BaSO4@X / WO3 particles, and the nano tungsten oxide is ICG-modified nano rod-shaped tungsten oxide, and the ICG-modified nano rod-shaped tungsten oxide is obtained by loading ICG; the barium sulfate is active barium sulfate obtained by surface activation treatment, and the surface activation treatment is silane coupling agent modification treatment, carboxylation treatment, surfactant modification treatment or mixing with barium chloride at a mass ratio of 1:0.02 - 0.1 and then treated by precipitation method.

2. A developing coating according to claim 1, characterized in that: The leveling agent is a fluorine-modified acrylic leveling agent, a natural oil leveling agent or a silicone leveling agent.

3. A developing coating according to claim 2, wherein: The wetting agent is a polyether wetting agent, a sugar derivative wetting agent or a silicone wetting agent.

4. A developing coating according to claim 3, wherein: The preparation of the BaSO4@X / WO3 particles includes the following steps: Step ① Add PVP to water or ethanol solution to obtain a dispersion solvent containing 1 - 3 wt% PVP; Step ② Put the ICG-modified nano rod-shaped tungsten oxide into the dispersion solvent for dispersion to obtain a tungsten oxide suspension containing 1 - 5 wt%, and put the barium sulfate into the dispersion solvent for dispersion to obtain a barium sulfate suspension containing 10 - 30 wt%; Step ③ Drop the tungsten oxide suspension into the stirred barium sulfate suspension, and continue to stir for 1 - 2 h after the dropping is completed to obtain a stirred composite liquid; Step ④ Let the stirred composite liquid stand for aging for 12 - 24 h, and then obtain the finished BaSO4@X / WO3 particles after centrifugation, washing with deionized water and drying in sequence.

5. A method for preparing a developing coating for preparing the developing coating according to any one of claims 1-4, characterized in that, It includes the following steps: Step 1, Prepare materials: Prepare acrylic resin, n-butanol, n-hexane, color paste, fumed silica, barium sulfate, nano tungsten oxide, leveling agent and wetting agent according to the corresponding mass percentages for standby. Step 2, Modification treatment: Subject the barium sulfate to surface activation treatment to obtain active barium sulfate, obtain ICG-modified nano rod-shaped tungsten oxide by loading ICG on the nano tungsten oxide, and then compound the active barium sulfate with the ICG-modified nano rod-shaped tungsten oxide to form BaSO4@X / WO3 particles for standby. Step 3, Mix for standby: Mix acrylic resin, n-butanol, n-hexane, color paste, fumed silica, leveling agent and wetting agent evenly, add BaSO4@X / WO3 particles and continue to stir and mix evenly to obtain the finished developing coating for standby.

6. The preparation method of a developing coating according to claim 5, characterized in that: The barium sulfate is surface-activated barium sulfate, and the surface activation treatment is silane coupling agent modification treatment, carboxylation treatment, surfactant modification treatment or mixing with barium chloride at a mass ratio of 1:0.02 - 0.1 and then treated by precipitation method.

7. The preparation method of a developing coating according to claim 6, characterized in that: The silane coupling agent is γ-aminopropyltriethoxysilane, and the modification treatment of the silane coupling agent includes adding γ-aminopropyltriethoxysilane and barium sulfate into ethanol, methanol or DMF, and stirring at 40-80 °C for 2-4 h to obtain surface-activated barium sulfate; the carboxylation treatment includes adding succinic anhydride and barium sulfate into DMSO, and stirring at 60-80 °C for 6-12 h to obtain activated barium sulfate; the precipitation method treatment includes adding barium sulfate and barium chloride into deionized water at a mass ratio of 1:0.02-0.1 for mixing, and then stirring and reacting at 50-70 °C to obtain surface-activated barium sulfate, and the concentrations of barium sulfate and barium chloride are 0.1-0.5 mol / L; the surface activation treatment also includes centrifugation, washing and precipitation, and dry barium sulfate is obtained.

8. The preparation method of a developing coating according to claim 5, characterized in that: The preparation of the ICG-modified nanorod tungsten oxide includes step ①: adding nanorod tungsten oxide into DMSO to disperse to obtain a tungsten oxide suspension containing 1-2 wt%, and adding ICG into ethanol to obtain a 1-10 wt% ICG solution; step ②: mixing and stirring the tungsten oxide suspension and the ICG solution to obtain a preliminary mixed material; step ③: performing ultrasonic treatment on the preliminary mixed material, controlling the ultrasonic treatment time to be 1-2 h and the power to be 100-300 W to obtain ICG-modified nanorod tungsten oxide.

9. Application of a developing coating, characterized in that: It includes using the developing coating according to any one of claims 1-4 and applying it to the production of a medical orthopedic imaging surgery positioning film.

10. The application of a developing coating according to claim 9, characterized in that: The medical orthopedic imaging surgery positioning film includes a medical adhesive, a permeable mesh and a polymer imaging film layer; the polymer imaging film layer is formed by coating and photo / thermal curing of the developing coating.

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