X-ray shielding coating, method of preparation and medical material containing same

Abstract

The application provides an X-ray shielding coating, which comprises gadolinium powder or its oxide 20-50 parts by weight, bismuth powder or its oxide 20-50 parts by weight, catechol 30-60 parts by weight, film-forming resin 70-90 parts by weight and auxiliary agent 1-10 parts by weight; more preferably, the X-ray shielding coating comprises gadolinium powder or its oxide 20-40 parts by weight, bismuth powder or its oxide 20-40 parts by weight, catechol 35-50 parts by weight, film-forming resin 80-90 parts by weight and auxiliary agent 1-5 parts by weight; a preparation method of the X-ray shielding coating comprises the following steps: S1. mixing gadolinium powder or its oxide and bismuth powder or its oxide uniformly, and adding a silane coupling agent into the mixture and performing ball milling; S2. dissolving the metal powder after surface treatment in a catechol solution to obtain a complex solution; S3. adding the complex solution into film-forming resin, then adding auxiliary agent, and dispersing for a period of time to obtain the X-ray shielding coating; and the application further provides an X-ray shielding medical material, which comprises a base material and the X-ray shielding coating coated on the surface of the base material; the obtained medical material has excellent X-ray shielding effect.

Description

Technical Field

[0001] This invention relates to the field of shielding materials technology, and more specifically, to an X-ray shielding coating, a preparation method thereof, and medical materials containing the same. Background Technology

[0002] X-rays are high-energy electromagnetic radiation waves with extremely strong penetrating power, and are widely used in medicine, industry, agriculture, national defense research, aerospace, environmental monitoring, and other fields. For example, in the medical field, X-rays are commonly used to create medical images to examine and diagnose diseases such as fractures, lung infections, and oral problems. However, prolonged exposure to X-rays can cause damage to the human body, therefore, necessary protective measures must be taken.

[0003] For example, gloves used in current medical interventional surgeries don't offer much X-ray shielding. Medical X-ray examination chest coverings are quite thick, making them inconvenient to use. Furthermore, security personnel on high-speed trains and subways often lack X-ray protective clothing.

[0004] Currently, lead and concrete are widely used as shielding materials in my country. Lead has a high density, good shielding performance, and is relatively inexpensive; however, lead has extremely poor structural strength, requiring a steel framework for larger shielding structures, otherwise it will collapse under its own weight. Furthermore, lead is a toxic heavy metal and is not heat-resistant, generating lead dust or vapor during processing and use, posing a significant hazard to personnel and organisms. An ideal X-ray shielding material should avoid lead introduction, meet shielding performance requirements, possess mechanical properties suitable for use, and exhibit good structural stability.

[0005] In existing technologies, some inorganic materials are used as shielding material coatings. However, the inorganic materials in the coating liquid are prone to uneven dispersion and agglomeration in the coating, which reduces the mechanical properties and protective performance of the coating after it is applied to medical materials. Summary of the Invention

[0006] To address the aforementioned problems, the present invention provides an X-ray shielding coating, comprising, by weight: 20-50 parts gadolinium powder or its oxide, 20-50 parts bismuth powder or its oxide, 30-60 parts catechol, 70-90 parts film-forming resin, and 1-10 parts additives; more preferably, comprising: 20-40 parts gadolinium powder or its oxide, 20-40 parts bismuth powder or its oxide, 35-50 parts catechol, 80-90 parts film-forming resin, and 1-5 parts additives.

[0007] A method for preparing the above-mentioned X-ray shielding coating is also provided, comprising the following steps:

[0008] S1. Mix gadolinium powder or its oxide and bismuth powder or its oxide evenly to obtain a mixed metal powder; mix 1-5% by mass of silane coupling agent (e.g., 3-aminopropyltriethoxysilane) and ethanol in equal proportions and add them to the above mixed metal powder, wherein the amount of silane coupling agent added is 0.5-1wt% of the mass of the mixed metal powder; ball mill for 12-24 hours and then dry; modify the gadolinium-bismuth metal powder to wet and activate the surface of the shielding agent, so that the particles are more evenly distributed in the system and avoid agglomeration;

[0009] S2. Dissolve the catechins completely under ultrasonic oscillation, dissolve the above surface-treated metal powder system in the catechin solution, adjust the pH to 3.0, and react at 20-40℃ for 12-24h to obtain a complex solution;

[0010] S3. Add the above complexing solution to the film-forming resin, stir and disperse for a period of time, then add the additives, and continue stirring and dispersing for a period of time to obtain the X-ray shielding coating.

[0011] An X-ray shielding medical material includes a substrate material and an X-ray shielding coating applied to the surface of the substrate material. The coating method is as follows: the substrate material is sequentially immersed in anhydrous ethanol, acetone, and deionized water for ultrasonic cleaning. After ultrasonic cleaning for 10 minutes, it is placed in an oven to dry for later use. Then, the treated substrate material is placed in the prepared X-ray shielding coating and impregnated with an equal volume method to ensure that the substrate material fully absorbs the coating. After removal, the substrate material is dehydrated and cured to obtain the X-ray shielding medical material.

[0012] The technical solutions of the embodiments of the present invention have at least the following advantages and beneficial effects:

[0013] This invention utilizes gadolinium powder or its oxide and bismuth powder or its oxide as functional particles, fully leveraging the K-layer boundary absorption effect of gadolinium and bismuth, resulting in a superior shielding effect against medical X-rays compared to lead. Furthermore, it utilizes catechol with ortho-phenolic hydroxyl structures to coordinate and crosslink with gadolinium and bismuth ions, forming stable five-membered chelate rings and a stable mesh structure. This allows for the stable complexation of more gadolinium and bismuth ions onto the film-forming resin, with high dispersibility. Ultimately, after the coating is applied to the substrate surface, the high affinity of catechol polyphenols adheres the gadolinium and bismuth to the substrate surface, improving the distribution of gadolinium and bismuth and overcoming the problem of poor protective effect caused by uneven dispersion. This results in better dispersion, higher loading, and better adhesion of gadolinium and bismuth ions, thus achieving a superior X-ray shielding effect. Detailed Implementation

[0014] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0015] The following is a detailed description of an X-ray shielding coating, its preparation method, and the medical material containing it provided by embodiments of the present invention.

[0016] An X-ray shielding coating, by weight, comprises: 20-50 parts gadolinium powder or its oxide, 20-50 parts bismuth powder or its oxide, 30-60 parts catechol, 70-90 parts film-forming resin, and 1-10 parts additives; more preferably, it comprises: 20-40 parts gadolinium powder or its oxide, 20-40 parts bismuth powder or its oxide, 35-50 parts catechol, 80-90 parts film-forming resin, and 1-5 parts additives.

[0017] Furthermore, the additives include, but are not limited to, film-forming agents, leveling agents, dispersants, silane coupling agents, defoamers, plasticizers, or wetting agents, with each component added in equal proportions.

[0018] Specifically, the film-forming aid can be 12-ol ester; the leveling agent can be a polyurethane rheology modifier, such as Dow Rohm and Haas RM-2020; the dispersant can be a sodium polycarboxylate dispersant, sodium polyacrylate, or ammonium polyacrylate; the defoamer can be an organosilicon or mineral oil; and the wetting agent can be a nonionic wetting agent.

[0019] Furthermore, the film-forming resin includes, but is not limited to, acrylic emulsions and waterborne polyurethane.

[0020] This invention utilizes gadolinium powder or its oxide and bismuth powder or its oxide as functional particles, fully leveraging the K-layer boundary absorption effect of gadolinium and bismuth, resulting in a superior shielding effect against medical X-rays compared to lead. Furthermore, it utilizes catechol with ortho-phenolic hydroxyl structures to coordinate and crosslink with gadolinium and bismuth ions, forming stable five-membered chelate rings and a stable mesh structure. This allows for the stable complexation of more gadolinium and bismuth ions onto the film-forming resin, with high dispersibility. Ultimately, after the coating is applied to the substrate surface, the high affinity of catechol polyphenols adheres the gadolinium and bismuth to the substrate surface, improving the distribution of gadolinium and bismuth and overcoming the problem of poor protective effect caused by uneven dispersion. This results in better dispersion, higher loading, and better adhesion of gadolinium and bismuth ions, thus achieving a superior X-ray shielding effect. In addition, the catechol groups can also undergo reactions such as Michael addition due to oxidation to crosslink into a gel, resulting in the simultaneous presence of coordination crosslinking and covalent crosslinking in the system. This allows the catechol to form two-coordinate and three-coordinate coordination crosslinking states with gadolinium and bismuth ions, which greatly improves the adhesion between the coating and the substrate.

[0021] The preparation method of the above-mentioned X-ray shielding coating includes the following steps:

[0022] S1. Mix gadolinium powder or its oxide and bismuth powder or its oxide evenly to obtain a mixed metal powder; mix 1-5% by mass of silane coupling agent (e.g., 3-aminopropyltriethoxysilane) and ethanol in equal proportions and add them to the above mixed metal powder, wherein the amount of silane coupling agent added is 0.5-1wt% of the mass of the mixed metal powder; ball mill for 12-24 hours and then dry; modify the gadolinium-bismuth metal powder to wet and activate the surface of the shielding agent, so that the particles are more evenly distributed in the system and avoid agglomeration;

[0023] S2. Dissolve the catechins completely under ultrasonic oscillation, dissolve the above surface-treated metal powder system in the catechin solution, adjust the pH to 3.0, and react at 20-40℃ for 12-24h to obtain a complex solution;

[0024] S3. Add the above complexing solution to the film-forming resin, stir and disperse for a period of time, then add the additives, and continue stirring and dispersing for a period of time to obtain the shielding coating.

[0025] An X-ray shielding medical material includes a matrix material and an X-ray shielding coating applied to the surface of the matrix material; the matrix material is a high-silica fiber cloth, latex, or rubber, such as one or more of natural latex, nitrile latex, chloroprene latex, polyurethane latex, ethylene propylene diene monomer (EPDM) rubber, butyl latex, polyisoprene, liquid silicone rubber, silicone rubber, and styrene-butadiene latex.

[0026] The coating method is as follows: The substrate material is placed in anhydrous ethanol, acetone and deionized water in sequence for ultrasonic cleaning. After ultrasonic cleaning for 10 minutes, it is placed in an oven to dry for later use. Then, the substrate material treated above is placed in the prepared X-ray shielding coating. The equal volume impregnation method is used to make the substrate material fully absorb the coating. After that, it is taken out, dehydrated and cured to obtain the X-ray shielding medical material.

[0027] Example 1

[0028] An X-ray shielding coating, by weight, comprises: 30 parts gadolinium powder, 30 parts bismuth powder, 40 parts catechol, 80 parts acrylic emulsion, 0.7 parts decyl alcohol ester, 0.5 parts Dow Rohm and Haas RM-202, 0.7 parts sodium polyacrylate, 0.5 parts silane coupling agent, 0.7 parts silicone defoamer, and 0.5 parts polyoxyethylene alcohol.

[0029] The preparation method of the above-mentioned X-ray shielding coating includes the following steps:

[0030] S1. Mix gadolinium powder or its oxide and bismuth powder or its oxide evenly to obtain a mixed metal powder; mix 1-5% by mass of silane coupling agent (e.g., 3-aminopropyltriethoxysilane) and ethanol in equal proportions and add them to the above mixed metal powder, wherein the amount of silane coupling agent added is 0.5-1wt% of the mass of the mixed metal powder; ball mill for 12-24 hours and then dry; modify the gadolinium-bismuth metal powder to wet and activate the surface of the shielding agent, so that the particles are more evenly distributed in the system and avoid agglomeration;

[0031] S2. Dissolve the catechins completely under ultrasonic oscillation, dissolve the above surface-treated metal powder system in the catechin solution, adjust the pH to 3.0, and react at 20-40℃ for 12-24h to obtain a complex solution;

[0032] S3. Add the above complexing solution to the film-forming resin, stir and disperse for a period of time, then add the additives, and continue stirring and dispersing for a period of time to obtain the shielding coating.

[0033] Preparation method of X-ray shielding medical material: The high-silica fiber cloth is placed in anhydrous ethanol, acetone and deionized water in sequence for ultrasonic cleaning. After ultrasonic cleaning for 10 minutes, it is placed in an oven to dry for later use. Then, the substrate material treated above is placed in the prepared X-ray shielding coating. The equal volume impregnation method is used to make the substrate material fully absorb the coating. After removal, it is dehydrated and cured to obtain the X-ray shielding medical material.

[0034] Example 2

[0035] The difference between this embodiment and Embodiment 1 is that the X-ray shielding coating, by weight, includes: 20 parts gadolinium powder, 20 parts bismuth powder, 30 parts catechol, 80 parts waterborne polyurethane, 0.8 parts dodecyl alcohol ester, 0.4 parts Dow Rohm and Haas RM-202, 0.7 parts sodium polycarboxylate, 1 part 3-aminopropyltriethoxysilane, 0.8 parts mineral oil, and 0.5 parts polyoxyethylene ether.

[0036] Example 3

[0037] The difference between this embodiment and Embodiment 1 is that the X-ray shielding coating, by weight, includes: 50 parts gadolinium powder, 50 parts bismuth powder, 60 parts catechol, 90 parts acrylic emulsion, 0.8 parts dodecyl alcohol ester, 0.4 parts Dow Rohm and Haas RM-202, 0.7 parts ammonium polyacrylate, 1 part 3-aminopropyltriethoxysilane, 0.8 parts mineral oil, and 0.5 parts polyoxyethylene alcohol.

[0038] Example 4

[0039] The difference between this embodiment and Embodiment 1 is that the X-ray shielding coating, by weight, includes: 20 parts gadolinium oxide, 20 parts bismuth oxide, 30 parts catechol, 80 parts acrylic emulsion, 0.8 parts dodecyl alcohol ester, 0.4 parts Dow Rohm and Haas RM-202, 0.8 parts ammonium polyacrylate, 1 part 3-aminopropyltriethoxysilane, 0.7 parts silicone defoamer, and 0.5 parts polyoxyethylene ether.

[0040] Example 5

[0041] The difference between this embodiment and Embodiment 1 is that the X-ray shielding coating, by weight, includes: 50 parts gadolinium oxide, 50 parts bismuth oxide, 60 parts catechol, 90 parts waterborne polyurethane, 1 part dodecyl alcohol ester, 0.5 parts Dow Rohm and Haas RM-202, 0.5 parts sodium polycarboxylate, 1 part 3-aminopropyltriethoxysilane, 0.8 parts mineral oil, and 0.9 parts polyoxyethylene ether.

[0042] Example 6

[0043] The difference between this embodiment and Embodiment 1 is that the X-ray shielding coating, by weight, includes: 35 parts gadolinium oxide, 35 parts bismuth oxide, 45 parts catechol, 85 parts waterborne polyurethane, 1.5 parts dodecyl alcohol ester, 0.5 parts Dow Rohm and Haas RM-202, 0.5 parts sodium polycarboxylate, 1 part 3-aminopropyltriethoxysilane, 1 part mineral oil, and 0.5 parts polyoxyethylene ether.

[0044] Comparative Example 1

[0045] The difference between this comparative example and Example 1 is that it does not contain catechins.

[0046] Comparative Example 2

[0047] The difference between this comparative example and Example 1 is that the metal powder contains only bismuth powder.

[0048] Comparative Example 3

[0049] The difference between this comparative example and Example 1 is that in the preparation method of the shielding coating, the metal powder is not modified in S1; that is, after the metal powder is mixed, it is dissolved in the catechol solution.

[0050] Experimental Example 1

[0051] The flexible gamma-ray shielding materials provided in Examples 1-6 and Comparative Examples 1-3 are designated as Experimental Groups 1-9, respectively; Specifications: 1m*1m (width*length); Thickness: 1mm;

[0052] The performance of the shielding coating was tested according to the People's Republic of China electronic industry standard SJ / T10674-1995 "General Technical Conditions for Coating". Radiation protection performance was tested according to GB / T9286-88 "Cross-cut Test of Paint and Varnish Film", GB 1768-79 "Method for Determination of Abrasion Resistance of Paint Film", and GBZ / T 147-2002 "Determination of Attenuation Performance of X-ray Protective Materials". X-ray shielding was tested using standard X-rays. The main physical properties of the shielding coating, including adhesion, pencil hardness, impact strength, abrasion resistance, and shielding effect, were tested. The test results are shown in Table 1.

[0053] Table 4. Test results of the main physical properties of the coating.

[0054]

[0055]

[0056] Therefore, it can be seen that the coating obtained by this invention, when applied to the surface of high-silica fiber cloth, exhibits good adhesion and wear resistance, meeting the needs of practical applications. Furthermore, the resulting X-ray shielding medical material demonstrates excellent shielding effect against X-rays and possesses superior overall performance. In contrast, the material obtained in the comparative example fails to meet the needs of practical applications, exhibiting poor performance in various aspects.

[0057] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An X-ray shielding coating, characterized in that, By weight, it includes: 20-50 parts of gadolinium powder or its oxide, 20-50 parts of bismuth powder or its oxide, 30-60 parts of catechol, 70-90 parts of film-forming resin, and 1-10 parts of additives. Gadolinium powder or its oxide, bismuth powder or its oxide, and catechol combine to form a five-membered chelate ring. The method for preparing the X-ray shielding coating includes the following steps: S1. Mix gadolinium powder or its oxide and bismuth powder or its oxide evenly to obtain a mixed metal powder; mix silane coupling agent and ethanol in equal proportions, add them to the above mixed metal powder, ball mill for a period of time, and then dry to obtain a metal powder system; S2. Dissolve the catechins completely under ultrasonic oscillation, dissolve the above metal powder system in the catechin solution, adjust the pH to 3.0, and react at 20-40℃ for 12-24h to obtain a complex solution; S3. Add the above complexing solution to the film-forming resin, stir and disperse for a period of time, then add the additives, and continue stirring and dispersing for a period of time to obtain the shielding coating.

2. The X-ray shielding coating according to claim 1, characterized in that, By weight, it includes: 20-40 parts gadolinium powder or its oxide, 20-40 parts bismuth powder or its oxide, 35-50 parts catechin, 80-90 parts film-forming resin, and 1-5 parts additives.

3. The X-ray shielding coating according to claim 2, characterized in that, The additives include film-forming agents, leveling agents, dispersants, silane coupling agents, and defoamers.

4. The X-ray shielding coating according to claim 2, characterized in that, The film-forming resin includes acrylic emulsion and waterborne polyurethane.

5. A method for preparing an X-ray shielding coating according to any one of claims 1-4, characterized in that, Includes the following steps: S1. Mix gadolinium powder or its oxide and bismuth powder or its oxide evenly to obtain a mixed metal powder; mix silane coupling agent and ethanol in equal proportions, add them to the above mixed metal powder, ball mill for a period of time, and then dry to obtain a metal powder system; S2. Dissolve the catechins completely under ultrasonic oscillation, dissolve the above metal powder system in the catechin solution, adjust the pH to 3.0, and react at 20-40℃ for 12-24h to obtain a complex solution; S3. Add the above complexing solution to the film-forming resin, stir and disperse for a period of time, then add the additives, and continue stirring and dispersing for a period of time to obtain the shielding coating.

6. The method for preparing the X-ray shielding coating according to claim 5, characterized in that, In S1, the mass fraction of the silane coupling agent is 1-5%.

7. The method for preparing the X-ray shielding coating according to claim 6, characterized in that, In S1, the amount of the silane coupling agent added is 0.5-1 wt% of the mass of the mixed metal powder.

8. A medical material for X-ray shielding, characterized in that, It includes a substrate material and an X-ray shielding coating as described in any one of claims 1-4, coated on the surface of the substrate material.

9. The X-ray shielding medical material according to claim 8, characterized in that, The matrix material is high-silica fiber cloth, latex, or rubber.

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