Medical catheter coating and use thereof

Abstract

The application belongs to the field of medical devices, and particularly relates to a medical catheter coating. The medical catheter coating comprises the following components in total amount parts: modified Cu-ZnO nanoparticles 10-15 parts; water-based PUA resin 25-35 parts; active diluent 10-25 parts; surfactant 1-1.5 parts; photoinitiator 1-2 parts; auxiliary agent 0.5-1 part; deionized water 10-20 parts; methanol and / or ethanol 40-60 parts. The coating provided by the application has good hydrophilicity, can reduce the friction between the catheter and human tissues, and has high antibacterial property.

Description

Technical Field

[0001] This invention belongs to the field of medical devices, specifically relating to a medical catheter coating and its application. Background Technology

[0002] Medical catheters are used in the treatment and diagnosis of various diseases and need to come into contact with human tissues, blood, and body fluids. Some even need to be implanted in the body for a long time. Therefore, there are extremely high requirements for the biocompatibility and antibacterial properties of medical catheters. Thus, it is of great significance to modify the surface of medical catheters to obtain biocompatibility and antibacterial properties.

[0003] Currently, the most common medical catheter materials on the market are polyvinyl chloride (PVC), polyurethane (PUA), and silicone rubber (SR), all of which are typically hydrophobic. When inserted into the body, these materials generate significant friction, often causing burning and pain in patients, damaging blood vessels and other tissues, and even triggering inflammation. Furthermore, bacteria that may adhere to the catheter surface can lead to infection. Clinically, a common solution is to apply a lubricant to the outer surface of the catheter to reduce friction between the catheter and human tissue. However, this method is not very effective, has poor durability, and is cumbersome to use, limiting its practical application. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide a medical catheter coating that has good hydrophilicity, can reduce the friction between the catheter and human tissue, and has high antibacterial properties.

[0005] The medical catheter coating comprises the following components in total parts:

[0006]

[0007] Furthermore, the reactive diluent is selected from one or more of PEG200DA, PEG300DA, PEG400DA and pentaerythritol triacrylate.

[0008] Furthermore, the surfactant is selected from one or more of polyvinylpyrrolidone K30, polyvinylpyrrolidone K60, and polyvinylpyrrolidone K90.

[0009] Furthermore, the photoinitiator is selected from one or more of photoinitiator 2959, photoinitiator TPO, and photoinitiator 1173D.

[0010] Furthermore, the additives include antioxidants and polymerization inhibitors.

[0011] Furthermore, the antioxidant is selected from antioxidant 168, and the polymerization inhibitor is selected from polymerization inhibitor 510.

[0012] Furthermore, the modified Cu-ZnO nanoparticles are prepared by the following method:

[0013] (1) Modification of ZnO nanoparticles: ZnO NPs were added to anhydrous ethanol and ultrasonically dispersed. After complete dispersion, silane coupling agent was added, and catalyst was added after stirring again. The reaction was continued at 40-60℃ for 2-3 hours. Then, the mixture was washed and stored in anhydrous ethanol for later use.

[0014] (2) Preparation of modified Cu-ZnO nanoparticles: The modified ZnO nanoparticles were dispersed in deionized water by ultrasonic dispersion. After complete dispersion, CuCl2·2H2O was added. The temperature was raised to 80℃ and the reducing agent was slowly added. The reaction was continued for 16-24h to obtain modified Cu-ZnO nanoparticles. The nanoparticles were washed with anhydrous ethanol and deionized water and then used.

[0015] Furthermore, the aqueous PUA resin is prepared by the following method:

[0016] Step 1: Add the reactant monomers hydroxyethyl acrylate (HEA) and isophorone diisocyanate (IPDI), stir well, then add the catalyst and antioxidant, and react at 30-50°C for 2-4 hours.

[0017] The second step involves adding PEG after the first step and continuing the reaction, with the functional group molar ratio of -NCO:-OH being 2:1. The same mass ratio of catalyst and antioxidant is added again, and the reaction is carried out at 60-80℃ for 3-5 hours to prepare waterborne PUA resin.

[0018] The present invention also provides the application of the medical catheter coating as described above in medical catheters.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] 1) Most medical catheters are made of polyurethane. Therefore, the water-based PUA resin in the coating can not only provide the coating with super hydrophilicity, but also effectively improve the adhesion between the coating and the catheter wall.

[0021] 2) Modifying ZnO nanoparticles with silane coupling agents can provide double bond reaction sites on the surface of ZnO nanoparticles, which can participate in the reaction during UV curing, thus better fixing Cu-ZnO nanoparticles in the coating.

[0022] 3) After modifying ZnO nanoparticles with KH-570, Cu particles are generated on their surface. The introduction of Cu particles can improve the antibacterial properties of ZnO nanoparticles and further fix the silane coupling agent modified on the surface of ZnO nanoparticles, so that the modification will not fall off during later use.

[0023] 4) ZnO nanoparticles have excellent antibacterial properties, but their antibacterial activity is weak under dark conditions. Introducing Cu particles on the surface of ZnO nanoparticles can effectively solve this problem. Cu-ZnO nanoparticles have highly efficient antibacterial properties.

[0024] 5) Introducing surfactants into the coating can further enhance the hydrophilicity of the coating itself, and on the other hand, it can play a lubricating role when the catheter comes into contact with human tissue. Attached Figure Description

[0025] Figure 1 The present invention provides a method for preparing modified Cu-ZnO nanoparticles.

[0026] Figure 2 The present invention provides a method for preparing waterborne PUA resin. Detailed Implementation

[0027] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but this should not be construed as limiting the scope of the present invention.

[0028] This invention provides a medical catheter coating, comprising the following components in total parts:

[0029]

[0030] Optionally, the reactive diluent is selected from one or more of PEG200DA, PEG300DA, PEG400DA and pentaerythritol triacrylate.

[0031] Optionally, the surfactant is selected from one or more of polyvinylpyrrolidone K30, polyvinylpyrrolidone K60, and polyvinylpyrrolidone K90. Introducing a surfactant into the coating can further enhance the hydrophilicity of the coating itself, and also provide lubrication when the catheter comes into contact with human tissue.

[0032] Optionally, the photoinitiator is selected from one or more of photoinitiator 2959, photoinitiator TPO, and photoinitiator 1173D. Using a composite photoinitiator can improve the curing efficiency of the coating and shorten the film formation time.

[0033] Optionally, the additives include antioxidants and polymerization inhibitors, wherein the antioxidant is selected from antioxidant 168 and the polymerization inhibitor is selected from polymerization inhibitor 510.

[0034] Methanol or ethanol can promote the compatibility of the components.

[0035] This invention first modifies ZnO nanoparticles with a silane coupling agent, and then generates Cu particles on their surface. Modifying ZnO nanoparticles with a silane coupling agent provides double bond reaction sites on the ZnO nanoparticle surface, which can participate in the reaction during UV curing, thus better fixing the Cu-ZnO nanoparticles in the coating. The introduction of Cu particles can, on the one hand, better enhance the antibacterial properties of ZnO nanoparticles, addressing the issue of weak antibacterial activity under dark conditions; on the other hand, it can further fix the silane coupling agent modified on the ZnO nanoparticle surface, preventing the modification from detaching during later use.

[0036] See Figure 1 The preparation process of modified Cu-ZnO nanoparticles is as follows:

[0037] (1) Modification of ZnO nanoparticles: ZnO NPs were added to anhydrous ethanol and ultrasonically dispersed. After complete dispersion, silane coupling agent was added, and catalyst was added after stirring again. The reaction was continued at 40-60℃ for 2-3 hours. Then, the mixture was washed and stored in anhydrous ethanol for later use.

[0038] (2) Preparation of modified Cu-ZnO nanoparticles: The modified ZnO nanoparticles were dispersed in deionized water by ultrasonic dispersion. After complete dispersion, CuCl2·2H2O was added. The temperature was raised to 80℃ and the reducing agent was slowly added. The reaction was continued for 16-24h to obtain modified Cu-ZnO nanoparticles. The nanoparticles were washed with anhydrous ethanol and deionized water and then used.

[0039] See Figure 2 The waterborne PUA resin is synthesized via a two-step reaction method, including the following steps:

[0040] Step 1: Add the reactant monomers hydroxyethyl acrylate (HEA) and isophorone diisocyanate (IPDI), stir well, then add the catalyst and antioxidant, and react at 30-50°C for 2-4 hours.

[0041] The second step involves adding PEG after the first step and continuing the reaction, with the functional group molar ratio of -NCO:-OH being 2:1. The same mass ratio of catalyst and antioxidant is added again, and the reaction is carried out at 60-80℃ for 3-5 hours to prepare waterborne PUA resin.

[0042] Most medical catheters are made of polyurethane, so the water-based PUA resin in the coating can not only provide the coating with superhydrophilicity, but also effectively improve the adhesion between the coating and the catheter wall.

[0043] Example 1

[0044] A medical catheter coating comprises the following raw materials in parts by weight:

[0045]

[0046] Preparation method of coating: Add the above raw materials to a 500mL three-necked beaker in sequence, and stir while sonicating in a 50℃ water bath for 30min, with ultrasonic power of 50% and stirring speed of 300rpm.

[0047] Preparation of hydrophilic coating: 500 μL of the coating stock solution was dropped onto a 5×5×2 mm PUA board. After the coating automatically leveled, it was tilted and allowed to stand for 2 minutes. Then, it was placed in a 60℃ oven for pre-baking for 5 minutes, followed by UV curing at a curing energy of 50000 mJ / cm². 2 .

[0048] Example 2

[0049] A medical catheter coating comprises the following raw materials in parts by weight:

[0050]

[0051] Preparation method of coating: Add the above raw materials to a 500mL three-necked beaker in sequence, and stir while sonicating in a 50℃ water bath for 30min, with ultrasonic power of 50% and stirring speed of 300rpm.

[0052] Preparation of hydrophilic coating: 500 μL of the coating stock solution was dropped onto a 5×5×2 mm PUA board. After the coating automatically leveled, it was tilted and allowed to stand for 2 minutes. Then, it was placed in a 60℃ oven for pre-baking for 5 minutes, followed by UV curing at a curing energy of 50000 mJ / cm². 2 .

[0053] Example 3

[0054] A medical catheter coating comprises the following raw materials in parts by weight:

[0055]

[0056] Preparation method of coating: Add the above raw materials to a 500mL three-necked beaker in sequence, and stir while sonicating in a 50℃ water bath for 30min, with ultrasonic power of 50% and stirring speed of 300rpm.

[0057] Preparation of hydrophilic coating: 500 μL of the coating stock solution was dropped onto a 5×5×2 mm PUA board. After the coating automatically leveled, it was tilted and allowed to stand for 2 minutes. Then, it was placed in a 60℃ oven for pre-baking for 5 minutes, followed by UV curing at a curing energy of 50000 mJ / cm². 2 .

[0058] Comparative Example 1

[0059] A medical catheter coating comprises the following raw materials in parts by weight:

[0060]

[0061] Preparation method of coating: Add the above raw materials to a 500mL three-necked beaker in sequence, and stir while sonicating in a 50℃ water bath for 30min, with ultrasonic power of 50% and stirring speed of 300rpm.

[0062] Preparation of hydrophilic coating: 500 μL of the coating stock solution was dropped onto a 5×5×2 mm PUA board. After the coating automatically leveled, it was tilted and allowed to stand for 2 minutes. Then, it was placed in a 60℃ oven for pre-baking for 5 minutes, followed by UV curing at a curing energy of 50000 mJ / cm². 2 .

[0063] Comparative Example 2

[0064] A medical catheter coating comprises the following raw materials in parts by weight:

[0065]

[0066] Preparation method of coating: Add the above raw materials to a 500mL three-necked beaker in sequence, and stir while sonicating in a 50℃ water bath for 30min, with ultrasonic power of 50% and stirring speed of 300rpm.

[0067] Preparation of hydrophilic coating: 500 μL of the coating stock solution was dropped onto a 5×5×2 mm PUA board. After the coating automatically leveled, it was tilted and allowed to stand for 2 minutes. Then, it was placed in a 60℃ oven for pre-baking for 5 minutes, followed by UV curing at a curing energy of 50000 mJ / cm². 2 .

[0068] In this invention, there was no significant difference in experimental results among different types of waterborne PUA resins.

[0069] Performance testing:

[0070] The coating performance of Examples 1-3 and Comparative Examples 1-2 was tested, including initial anti-fogging performance, anti-fogging performance after immersion, water contact angle, hardness, adhesion, and abrasion resistance.

[0071] The specific performance test items and corresponding methods are as follows:

[0072] I. Water contact angle test:

[0073] 2.5 μL of ultrapure water was dropped onto the surface of the cured film, and the test was performed at room temperature using a contact angle meter.

[0074] II. Adhesion Test:

[0075] The adhesion of the samples was tested using the white grid method with 3M self-adhesive tape.

[0076] Assessment Method:

[0077] Grade 0 - The edges of the scribing lines are smooth, and there is no paint film peeling at the edges and intersections of the scribing lines;

[0078] Level 1 - Small patches of paint film have peeled off at the intersection of the lines, but the peeled area is less than 5%;

[0079] Level 2 - Small patches of paint film have peeled off at the edges and intersections of the lines, but the peeled area is between 5% and 15%.

[0080] Level 3 - There are patches of paint film peeling off at the edges and intersections of the lines, but the peeling area is between 15% and 35%.

[0081] Level 4 - There are patches of paint film peeling off at the edges and intersections of the lines, but the peeling area is between 35% and 65%.

[0082] Level 5 - There are patches of paint film peeling off at the edges and intersections of the lines, but the peeling area is greater than 65%.

[0083] III. Antibacterial test:

[0084] The antibacterial properties of the coating were evaluated by measuring the proliferation of bacterial colonies using the plate count method, according to the antibacterial test method specified in GB / T 21866-2008 "Determination of Antibacterial Properties and Antibacterial Effects of Antibacterial Coatings (Films)". Gram-positive bacteria (ATCC 547) and Gram-negative bacteria (ATCC 1555) were selected as the target test species.

[0085] Table 1 Comparison of performance parameters in Examples 1-5

[0086]

[0087]

[0088] Results analysis:

[0089] Compared to Example 1, Example 2 changed the active diluent used from PEG200DA to PEG400DA. The composition ratio of the coating, especially the proportion of nanoparticles, was slightly increased, resulting in a small difference in the water contact angle. This difference is generally considered to be consistent (<10°) on a macroscopic coating performance scale and has little impact on lubrication functionality.

[0090] Compared to Example 1, Example 3 uses a different monomer than PEG200DA, which is pentaerythritol triacrylate. This results in a lower water contact angle for the coating in Example 3 compared to Example 1.

[0091] Compared to Comparative Example 1 and Example 3, the nanoparticles were not modified to introduce copper, resulting in a weaker antibacterial effect in the final coating compared to the modified Cu-ZnO nanoparticles used in Example 3.

[0092] Compared with Comparative Example 2 and Example 1, the coating does not contain modified Cu-ZnO nanoparticles, therefore the prepared coating does not have antibacterial properties.

Claims

1. A medical catheter coating, characterized in that, The components include the following parts by weight: 10-15 parts of modified Cu-ZnO nanoparticles; 25-35 parts of water-based PUA resin; 10-25 parts of reactive diluent; 1 to 1.5 parts of surfactant; 1-2 parts of photoinitiator; Additives: 0.5–1 part; 10-20 parts deionized water; 40-60 parts of methanol and / or ethanol; The reactive diluent is selected from one or more of PEG200DA, PEG300DA, PEG400DA and pentaerythritol triacrylate; The surfactant is selected from one or more of polyvinylpyrrolidone K30, polyvinylpyrrolidone K60 and polyvinylpyrrolidone K90; The modified Cu-ZnO nanoparticles were prepared by the following method: (1) Modification of ZnO nanoparticles: ZnO NPs were added to anhydrous ethanol and ultrasonically dispersed. After complete dispersion, a silane coupling agent was added, and after stirring again, a catalyst was added. The reaction was continued at 40-60℃ for 2-3 hours. Then, the mixture was washed and stored in anhydrous ethanol for later use. The silane coupling agent was KH-570. (2) Preparation of modified Cu-ZnO nanoparticles: The modified ZnO nanoparticles were dispersed in deionized water by ultrasonic dispersion. After complete dispersion, CuCl2•2H2O was added. The temperature was raised to 80℃ and the reducing agent was slowly added. The reaction was continued for 16-24h to obtain modified Cu-ZnO nanoparticles. The nanoparticles were washed with anhydrous ethanol and deionized water and then used. The aqueous PUA resin is prepared by the following method: Step 1: Add the reactant monomers hydroxyethyl acrylate and isophorone diisocyanate, stir well, then add the catalyst and antioxidant, and react at 30-50°C for 2-4 hours; The second step involves adding PEG after the first step and continuing the reaction, with the functional group molar ratio of -NCO:-OH being 2:

1. The same mass ratio of catalyst and antioxidant is added again, and the reaction is carried out at 60-80℃ for 3-5 hours to prepare waterborne PUA resin.

2. The medical catheter coating as described in claim 1, characterized in that, The photoinitiator is selected from one or more of photoinitiator 2959, photoinitiator TPO, and photoinitiator 1173D.

3. The medical catheter coating as described in claim 1, characterized in that, The additives include antioxidants and polymerization inhibitors.

4. The medical catheter coating as described in claim 3, characterized in that, The antioxidant is selected from antioxidant 168, and the polymerization inhibitor is selected from polymerization inhibitor 510.

5. The application of the medical catheter coating as described in claim 1 in the preparation of medical catheters.

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