A high-toughness ultra-slip coating and its preparation method and application

Abstract

The present invention belongs to the field of medical device technology, and relates to a high-toughness ultra-slip coating and its preparation method and application. The coating includes a base layer and a surface layer, and is prepared by immersing a latex / silicone catheter in the base layer coating and the surface layer coating in turn for a certain period of time, and then curing with ultraviolet light; the benzophenone derivative in the base layer can extract hydrogen protons from the substrate to generate free radicals under ultraviolet light, and the vinyl acetate structure in the base layer plays a viscosity-increasing role. After synergizing with the aforementioned hydrogen extraction effect, the base layer can be firmly attached to the substrate through covalent bonds; the benzophenone-modified double network structure compound in the surface layer can be firmly connected to the base layer under ultraviolet light, forming an ultra-slip coating with high toughness, high lubricity and excellent durability that penetrates each other, which can remain intact and undamaged during the water-filled expansion process of the catheter balloon. The coating has high biocompatibility and can effectively reduce the risk of expansion and shedding of the coating of the catheter during clinical use.

Description

Technical Field

[0001] The invention belongs to the technical field of medical devices and relates to a high-toughness ultra-slip coating and a preparation method and application thereof. Background Art

[0002] The catheter is a Class II interventional medical device product, and catheterization technology is an invasive procedure in clinical practice. During its use, it will cause discomfort, pain and urethral trauma to patients. Therefore, doctors initially used lubricants with catheters to reduce the friction between the catheter and the urethral mucosa, thereby minimizing the risk of surgery. Later, the use of lubricants was cumbersome, not conducive to operation, and had poor lubrication properties, making it difficult to maintain lubricity for a long time. In addition, improper use of lubricants can cause the balloon-carrying catheter to burst, causing surgical risks, so hydrophilic lubricating catheter coatings came into being.

[0003] Secondly, most of the catheters used in the market are latex / silicone catheters with balloons. In order to avoid the risk of the coating on the catheter balloon breaking and falling off after expanding to a certain volume during surgery, the toughness requirements of the coating become more stringent. At the same time, the lubricity and stability of the coating on the catheter must also be maintained. In the prior art, although there are many medical device surface lubricating coatings, on the one hand, there are still deficiencies in the toughness of the lubricating coating; on the other hand, there are relatively few durable light-cured lubricating coating technologies for low surface energy silicone materials. Summary of the invention

[0004] To achieve the above object, the present invention adopts the following technical solutions:

[0005] The invention provides a high-toughness ultra-slip coating, comprising a base layer and a surface layer, which is prepared by immersing a substrate in a base layer coating and a surface layer coating in sequence for a certain period of time and curing the substrate with ultraviolet light. The coating is characterized in that the base layer coating has a viscosity of 1.52 mPa•S-3.72 mPa•S, and uses a vinyl benzophenone derivative 1, an active diluent and an organic solvent as main raw materials; wherein the addition amounts of the vinyl benzophenone derivative 1, the active diluent and the organic solvent are 2%-5%, 0.7%-1.5% and 93.5%-97.3% of the total mass of the base layer coating, respectively; the surface layer coating has a viscosity of 30.7 mPa•S-48.5 mPa•S, and uses a vinyl benzophenone derivative 2 double network structure compound, an active diluent and an organic solvent as main raw materials; wherein the addition amounts of the vinyl benzophenone derivative 2 double network structure compound, the active diluent and the organic solvent are 2%-5%, 0.5%-1.5% and 93.5%-97.5% of the total mass of the surface layer coating, respectively.

[0006] Furthermore, the vinyl benzophenone derivative 1 uses vinyl acetate monomer, vinyl benzophenone monomer, thermal initiator and vinyl silane coupling agent monomer as main raw materials; wherein the molar ratio of vinyl acetate monomer, vinyl benzophenone monomer and vinyl silane coupling agent monomer is (0.03-0.045):(0.25-0.75):(0.5-1); the content of thermal initiator is 0.5%-2% of the total mass of each monomer; the molecular structure schematic diagram of the vinyl benzophenone derivative 1 is shown in Figure A or B below, wherein e, f, g are the number of structural units of the polymer:

[0007]

[0008] From the chemical structure shown above, the following three points are used to explain the mechanism of action of the vinyl benzophenone derivative 1 in the bottom layer: First, the benzophenone part acts as a photoinitiator group. Under the irradiation of ultraviolet light, it can extract hydrogen protons from the substrate to generate free radicals, thereby attacking the carbonyl bond to open the carbonyl bond and generate oxygen anions. The oxygen anions capture hydrogen protons to form hydroxyl groups. This process forms a covalent bond between the benzophenone part and the substrate and firmly adheres to the substrate. In addition, it can also trigger the cross-linking reaction of the diluent monomer in the bottom layer. Second, the polymer formed by copolymerization with vinyl acetate can provide excellent adhesion and durability. Third, the silane coupling agent itself can be used as an adhesion promoter, and the polymer formed by copolymerization with the silane coupling agent can provide a certain number of polar groups after hydrolysis, thereby improving the adhesion between the bottom layer and the substrate.

[0009] Furthermore, the vinyl benzophenone derivative 2 double network structure compound uses acrylamide monomer, vinyl benzophenone monomer, thermal initiator, vinyl silane coupling agent monomer and polyvinyl pyrrolidone as main raw materials: the molar ratio of vinyl benzophenone monomer, acrylamide monomer and vinyl silane coupling agent monomer is (0.03-0.045): (0.5-1): (0.1-0.3); the content of thermal initiator is 0.5%-2% of the total mass of each monomer; the amount of polyvinyl pyrrolidone added is 50%-80% of the total mass of the solution; the chemical structure schematic diagram of the vinyl benzophenone derivative 2 double network structure compound is shown in Figure C or D below:

[0010]

[0011] From the chemical structure shown above, the following three points are used to explain the mechanism of action of the double network structure compound of the vinyl benzophenone derivative in the surface layer: First, the benzophenone part acts as a photoinitiator group, which can trigger the cross-linking reaction of the diluent monomer in the surface layer under the irradiation of ultraviolet light; second, the polymer formed by copolymerization with acrylamide can provide excellent lubricity; third, the silane coupling agent itself can be used as an adhesion promoter, and the polymer formed by copolymerization with the silane coupling agent can provide a certain number of polar groups after hydrolysis, thereby improving the adhesion between the bottom layer and the surface layer. In addition, after the intermolecular entanglement between the structural compound and polyvinyl pyrrolidone, the toughness and lubricity of the coating can be improved to a certain extent. The present invention also provides a method for preparing a high-toughness ultra-slip coating, characterized in that it comprises the following steps:

[0012] Step A, preparation of vinyl benzophenone derivative 1: adding a certain molar mass of vinyl acetate monomer to a reaction vessel, adding anhydrous ethanol, vinyl benzophenone monomer, and a thermal initiator, heating and stirring under nitrogen protection, then dropwise adding a vinyl silane coupling agent monomer, continuing to stir after heating, and stopping heating when the reaction is completed to prepare a vinyl benzophenone derivative 1.

[0013] Step B, preparation of a double network structure compound of a vinyl benzophenone derivative 2: adding a certain molar mass of acrylamide monomer to a reaction container, adding anhydrous ethanol, vinyl benzophenone monomer, and a thermal initiator, heating and stirring under nitrogen protection, then dropping a vinyl silane coupling agent monomer, continuing to stir after heating, and simultaneously adding a certain mass of polyvinyl pyrrolidone ethanol solution, continuing to stir and react for a period of time, stopping heating when the reaction is completed, and preparing a double network structure compound of a vinyl benzophenone derivative 2.

[0014] Step C, preparation of the base coating: dissolve the vinyl benzophenone derivative 1 prepared in step A and the active diluent in an organic solvent or water, and stir for 2 hours at room temperature in the dark to obtain the base coating.

[0015] Step D, preparation of the surface coating: dissolve the vinyl benzophenone derivative 2 double network structure compound prepared in step B and the active diluent in an organic solvent or water, and stir for 4 hours at room temperature in the dark to obtain the surface coating.

[0016] Step E, preparation of high-toughness ultra-smooth coating: first, dip the substrate into the base coating, and form a base layer after soaking and UV curing; then dip the substrate with the base layer into the surface coating, and form a high-toughness ultra-smooth coating after soaking and UV curing.

[0017] Furthermore, the vinyl benzophenone monomer described in step A and step B includes any one of 4-acryloxybenzophenone, 4-vinyloxybenzophenone, 4-acrylamidebenzophenone, 4-propyleneoxybenzophenone, and 4-methacryloxybenzophenone; the thermal initiator includes any one of azobisisobutyronitrile and benzoyl peroxide; the vinyl silane coupling agent monomer includes any one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane and γ-methacryloxypropyltrimethoxysilane; the number average molecular weight of the polyvinyl pyrrolidone described in step B is between 600,000 and 1.3 million.

[0018] Furthermore, the active diluent in step C and step D includes any one or two of polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, furan acrylate and isobornyl acrylate; and the organic solvent includes any one or two of ethanol and isopropanol.

[0019] Furthermore, in step E, the substrate is dipped in the primer for 10s-60s, and the UV lamp irradiation time is 60s-120s; the substrate is dipped in the surface coating for 10s-60s, and the UV lamp irradiation time is 100s-240s; the substrate includes any one of a latex catheter, a silicone catheter, a polyurethane catheter, and a polyvinyl chloride catheter.

[0020] The present invention also provides an application method of a high-toughness super-slip coating for improving the performance of a balloon catheter, characterized in that the friction coefficient of the catheter containing the coating is reduced by 99.1%-99.9% compared with an uncoated blank balloon catheter, and after 1000 frictions, the friction coefficient is stabilized between 0.01-0.04; after the balloon at the front end of the catheter is inflated, the coating on the balloon remains intact and without cracks.

[0021] The beneficial effects of the present invention are:

[0022] 1. The high-toughness ultra-slip coating provided by the present invention comprises two layers, namely a bottom layer and a surface layer. The benzophenone derivative in the bottom layer can extract hydrogen protons from the catheter substrate to generate free radicals under ultraviolet light irradiation, and the vinyl acetate structure in the bottom layer plays a viscosity-increasing role. After synergizing with the aforementioned hydrogen extraction effect, the bottom layer can be firmly attached to the substrate through covalent bonds; the benzophenone-modified double network structure compound in the surface layer can be firmly connected to the bottom layer under ultraviolet light irradiation, forming an ultra-slip coating with high toughness, high lubricity and excellent durability that penetrates each other, and the coating has high biocompatibility, which can effectively reduce the risk of expansion and shedding of the coating during clinical use of the catheter.

[0023] 2. The high-toughness ultra-slip coating provided by the present invention can be firmly attached to catheters of different materials, especially for catheters made of silicone with low surface energy and poor adhesion. Without any pre-treatment (including plasma treatment and chemical treatment), the coating can be firmly attached to the silicone substrate. Similarly, it is more feasible for catheters made of latex with higher surface energy. Brief description: The catheter is coated with the high-toughness ultra-slip coating of the present invention and cured under ultraviolet light. Compared with the uncoated blank balloon catheter, the friction coefficient is reduced by 99.1%-99.9%, and after 1000 frictions, the friction coefficient is stabilized between 0.01-0.04, proving the high firmness of the coating.

[0024] 3. With regard to the balloon part at the front end of the catheter, according to the clinical use scenario, the coating on the balloon needs to expand to a certain extent with the expansion of the balloon without breaking or falling off; the high-toughness super-slip coating of the present invention solves this problem, thereby avoiding the surgical risks caused by the indwelling catheter.

[0025] 4. The high-toughness ultra-slip coating provided by the present invention can be cured within a few minutes under the irradiation of ultraviolet light, and the coating is easy to store, which is beneficial to improving production efficiency and reducing costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solution of the present invention, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0027] Figure 1 : are performance test diagrams of latex catheters, wherein a is a friction coefficient test diagram of an uncoated blank latex catheter, b is a friction coefficient test diagram of a coated latex catheter prepared in Example 3, and c is a front end balloon expansion test diagram of a coated latex catheter prepared in Example 3.

[0028] Figure 2 : are performance test diagrams of silicone urinary catheters, wherein a is a friction coefficient test diagram of a blank silicone urinary catheter without coating, b is a friction coefficient test diagram of a coated silicone urinary catheter prepared in Example 3, and c is a front end balloon expansion test diagram of a coated silicone urinary catheter prepared in Example 3.

[0029] Figure 3 These are performance test diagrams of the coated latex urinary catheter prepared in Comparative Example 1, wherein a is a friction coefficient test diagram and b is a front end balloon expansion test diagram.

[0030] Figure 4 These are performance test diagrams of the coated silicone urinary catheter prepared in Comparative Example 1, wherein a is a friction coefficient test diagram and b is a front end balloon expansion test diagram.

[0031] Figure 5 These are performance test diagrams of the coated latex urinary catheter prepared in Comparative Example 2, wherein a is a friction coefficient test diagram and b is a front end balloon expansion test diagram.

[0032] Figure 6 These are performance test diagrams of the coated silicone urinary catheter prepared in Comparative Example 2, where a is a friction coefficient test diagram and b is a front end balloon expansion test diagram. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. The embodiments mentioned are all implemented on the premise of the technical solutions of the present invention, and detailed implementation processes are given, but it should be stated that the protection scope of the present invention is not limited to the following embodiments.

[0034] Preparation Example (I):

[0035] Preparation of 4-acryloyloxybenzophenone derivative 1: Add 0.4 mmol of vinyl acetate to a 25 ml round-bottom flask, then add 3 ml of anhydrous ethanol, 0.03 mmol of 4-acrylate benzophenone, and 1% of azobisisobutyronitrile, place in an oil bath at 60 ° C under nitrogen protection and stir for 30 min, then add 0.5 mmol of vinyltrimethoxysilane dropwise to the round-bottom flask, heat to 80 ° C and stir for 6 hours, then stop the reaction and cool to room temperature to obtain 4-acrylate benzophenone derivative 1.

[0036] Preparation of double network structure compound of 4-acryloxybenzophenone derivative 2: Add 0.8 mmol of acrylamide to a 25 ml round-bottom flask, then add 3 ml of anhydrous ethanol, 0.04 mmol of 4-acryloxybenzophenone, and 0.8% of azobisisobutyronitrile, place in an oil bath at 60 ° C under nitrogen protection and stir for 30 min, then add 0.2 mmol of vinyltrimethoxysilane dropwise to the round-bottom flask, heat to 80 ° C and stir for 30 min, then add 1.5 g of polyvinylpyrrolidone ethanol solution, continue stirring and react for 6 h, stop the reaction and cool to room temperature to obtain the double network structure compound of 4-acryloxybenzophenone derivative 2.

[0037] The following Examples 1-3 all use the double network structure compounds of 4-acryloxybenzophenone derivative 1 and 4-acryloxybenzophenone derivative 2 prepared in the above-mentioned preparation Example (I) as raw materials for preparing the coating liquid. Example

[0038] (1) 4-Acryloxybenzophenone derivative 1, polyethylene glycol diacrylate 1000, and ethoxylated trimethylol triacrylate are dissolved in a mixed solvent of ethanol and deionized water, and stirred for 2 hours at room temperature in the dark to obtain a primer; wherein the amount of 4-acryloxybenzophenone derivative 1 added is 3% of the total mass of the primer, the mass of polyethylene glycol diacrylate 1000 is 0.8% of the total mass of the primer, the mass of ethoxylated trimethylol triacrylate is 0.4% of the total mass of the primer, and the mass of ethanol and deionized water is 95.8% of the total mass of the primer.

[0039] (2) Dissolving 4-acryloxybenzophenone derivative 2 double network structure compound and polyethylene glycol diacrylate 1000 in a mixed solvent of ethanol and deionized water, stirring for 4 hours at room temperature in the dark, thereby obtaining a top coating; wherein the addition amount of 4-acryloxybenzophenone derivative 2 double network structure compound is 3% of the total mass of the top coating, the mass of polyethylene glycol diacrylate 1000 is 0.6% of the total mass of the top coating, and the mass of ethanol and deionized water is 96.4% of the total mass of the top coating.

[0040] (3) The latex / silicone catheter is dipped in the base coating for 20 seconds, and then irradiated with a UV lamp for 90 seconds. The base coating is then cured on the latex / silicone catheter to form a base layer. The latex / silicone catheter with the base layer is then dipped in the top coating for 20 seconds, and irradiated with a UV lamp for 150 seconds. After the top coating is cured, an ultra-slip coating with high toughness, high lubricity and excellent durability is formed on the latex / silicone catheter. Example

[0041] (1) 4-acryloxybenzophenone derivative 1 and ethoxylated trimethylolpropane triacrylate are dissolved in a mixed solvent of ethanol and deionized water, and stirred for 2 hours at room temperature in the dark to obtain a primer; wherein the amount of 4-acryloxybenzophenone derivative 1 added is 4% of the total mass of the primer, the mass of ethoxylated trimethylolpropane triacrylate is 1% of the total mass of the primer, and the mass of ethanol and deionized water is 95% of the total mass of the primer.

[0042] (2) Dissolve 4-acryloxybenzophenone derivative 2 double network structure compound, ethoxylated trimethylolpropane triacrylate and polyethylene glycol diacrylate 1000 in a mixed solvent of ethanol and deionized water, and stir for 4 hours at room temperature in the dark to obtain a top coating; wherein the amount of 4-acryloxybenzophenone derivative 2 double network structure compound added is 4% of the total mass of the top coating, the mass of ethoxylated trimethylolpropane triacrylate is 0.4% of the total mass of the top coating, the mass of polyethylene glycol diacrylate 1000 is 0.6% of the total mass of the top coating, and the mass of ethanol and deionized water is 95% of the total mass of the top coating.

[0043] (3) The latex / silicone catheter was dipped in the base coating for 10 seconds, and then irradiated with a UV lamp for 60 seconds. Then, the base coating was cured on the latex / silicone catheter to form a base layer. Then, the latex / silicone catheter with the base layer was dipped in the top coating for 10 seconds, and irradiated with a UV lamp for 180 seconds. After the top coating was cured, an ultra-slip coating with high lubricity, high toughness and excellent durability was formed on the latex / silicone catheter. Example

[0044] (1) 4-acryloxybenzophenone derivative 1, 1,6-hexanediol diacrylate and furan acrylate are dissolved in a mixed solvent of ethanol and deionized water, and stirred for 2 hours at room temperature in the dark to obtain a primer; wherein the amount of 4-acryloxybenzophenone derivative 1 added is 3% of the total mass of the primer, the mass of 1,6-hexanediol diacrylate is 0.4% of the total mass of the primer, the mass of furan acrylate is 0.3% of the total mass of the primer, and the mass of ethanol and deionized water is 96.3% of the total mass of the primer.

[0045] (2) Dissolve 4-acryloxybenzophenone derivative 2 double network structure compound, 1,6-hexanediol diacrylate and furan acrylate in a mixed solvent of ethanol and deionized water, and stir for 4 hours at room temperature in the dark to obtain a top coating; wherein the amount of 4-acryloxybenzophenone derivative 2 double network structure compound added is 3% of the total mass of the top coating, the mass of 1,6-hexanediol diacrylate is 0.4% of the total mass of the top coating, the mass of furan acrylate is 0.3% of the total mass of the top coating, and the mass of ethanol and deionized water is 96.3% of the total mass of the top coating.

[0046] (3) The latex / silicone catheter is dipped in the base coating for 30 seconds, and then irradiated with a UV lamp for 100 seconds. Then, the base coating is cured on the latex / silicone catheter to form a base layer. Then, the latex / silicone catheter with the base layer is dipped in the top coating for 30 seconds, and irradiated with a UV lamp for 200 seconds. After the top coating is cured, an ultra-slip coating with high toughness, high lubricity and excellent durability is formed on the latex / silicone catheter.

[0047] Preparation Example (II):

[0048] Preparation of 4-acrylamide benzophenone derivative 1: Add 0.75 mmol of vinyl acetate to a 25 ml round-bottom flask, then add 3 ml of anhydrous ethanol, 0.045 mmol of 4-acrylamide benzophenone, and 2% of azobisisobutyronitrile, place in an oil bath at 60 ° C under nitrogen protection and stir for 30 min, then add 0.5 mmol of γ-methacryloxypropyltrimethoxysilane dropwise to the round-bottom flask, heat to 80 ° C and stir for 6 h, then stop the reaction and cool to room temperature to obtain 4-acrylamide benzophenone derivative 1.

[0049] Preparation of double network structure compound of 4-acrylamide dibenzophenone derivative 2: Add 1 mmol of acrylamide to a 25 ml round-bottom flask, then add 3 ml of anhydrous ethanol, 0.04 mmol of 4-acrylamide dibenzophenone, and 1% of azobisisobutyronitrile, place in an oil bath at 60 ° C under nitrogen protection and stir for 30 min, then add 0.3 mmol of γ-methacryloxypropyltrimethoxysilane dropwise to the round-bottom flask, heat to 80 ° C and stir for 30 min, then add 1.6 g of polyvinyl pyrrolidone ethanol solution, continue stirring the reaction for 6 hours, stop the reaction and cool to room temperature to obtain the double network structure compound of 4-acryloxy dibenzophenone derivative 2.

[0050] The following Examples 4 and 5 both use the double network structure compounds of 4-acrylamide benzophenone derivative 1 and 4-acrylamide benzophenone derivative 2 prepared in the above-mentioned Preparation Example (II) as raw materials for preparing the coating liquid. Example

[0051] (1) 4-acrylamide benzophenone derivative 1 and pentaerythritol triacrylate are dissolved in a mixed solvent of ethanol and deionized water, and stirred for 2 hours at room temperature in the dark to obtain a primer; wherein the amount of 4-acrylamide benzophenone derivative 1 added is 3% of the total mass of the primer, the mass of pentaerythritol triacrylate is 0.4% of the total mass of the primer, and the mass of ethanol and deionized water is 96.6% of the total mass of the primer.

[0052] (2) Dissolve 4-acrylamide benzophenone derivative 2 double network structure compound, pentaerythritol triacrylate and isobornyl acrylate in a mixed solvent of ethanol and deionized water, and stir for 4 hours at room temperature in the dark to obtain a top coating; wherein the amount of 4-acrylamide benzophenone derivative 2 double network structure compound added is 3% of the total mass of the top coating, the mass of pentaerythritol triacrylate is 0.5% of the total mass of the top coating, the mass of isobornyl acrylate is 0.3% of the total mass of the top coating, and the mass of ethanol and deionized water is 96.2% of the total mass of the top coating.

[0053] (3) The latex / silicone catheter is dipped in the base coating for 30 seconds, and then irradiated with a UV lamp for 100 seconds. Then, the base coating is cured on the latex / silicone catheter to form a base layer. Then, the latex / silicone catheter with the base layer is dipped in the top coating for 30 seconds, and irradiated with a UV lamp for 200 seconds. After the top coating is cured, an ultra-slip coating with high toughness, high lubricity and excellent durability is formed on the latex / silicone catheter. Example

[0054] (1) 4-Acrylamide benzophenone derivative 1, pentaerythritol triacrylate and isobornyl acrylate are dissolved in a mixed solvent of ethanol and deionized water, and stirred for 2 hours at room temperature in the dark to obtain a primer; wherein the amount of 4-acrylamide benzophenone derivative 1 added is 3% of the total mass of the primer, the mass of pentaerythritol triacrylate is 0.3% of the total mass of the primer, the mass of isobornyl acrylate is 0.4% of the total mass of the primer, and the mass of ethanol and deionized water is 96.3% of the total mass of the primer.

[0055] (2) Dissolve 4-acrylamide benzophenone derivative 2 double network structure compound and pentaerythritol triacrylate in a mixed solvent of ethanol and deionized water, and stir for 4 hours at room temperature in the dark to obtain a top coating; wherein the amount of 4-acrylamide benzophenone derivative 2 double network structure compound added is 3% of the total mass of the top coating, the mass of pentaerythritol triacrylate is 0.5% of the total mass of the top coating, and the mass of ethanol and deionized water is 96.5% of the total mass of the top coating.

[0056] (3) The latex / silicone catheter is dipped in the base coating for 30 seconds, and then irradiated with a UV lamp for 100 seconds. Then, the base coating is cured on the latex / silicone catheter to form a base layer. Then, the latex / silicone catheter with the base layer is dipped in the top coating for 30 seconds, and irradiated with a UV lamp for 200 seconds. After the top coating is cured, an ultra-slip coating with high toughness, high lubricity and excellent durability is formed on the latex / silicone catheter.

[0057] Comparative Example 1

[0058] (1) The 4-acryloxybenzophenone derivative 1 is replaced with polyvinyl acetate with a molecular weight of 500,000, and then the polyvinyl acetate and polyethylene glycol diacrylate 1000 are dissolved in a mixed solvent of ethanol and deionized water. After stirring for 2 hours at room temperature in the dark, benzophenone photoinitiator is added and stirring is continued for 30 minutes to obtain a primer; wherein the amount of polyvinyl acetate added is 3% of the total mass of the primer, the mass of polyethylene glycol diacrylate 1000 is 0.7% of the total mass of the primer, the mass of benzophenone is 5% of the mass of polyethylene glycol diacrylate, the mass of ethanol and deionized water is 96.3% of the total mass of the primer, and the mass ratio of ethanol to deionized water is 9:1.

[0059] (2) Dissolve 4-acryloxybenzophenone derivative 2 double network structure compound and polyethylene glycol diacrylate 1000 in a mixed solvent of ethanol and deionized water, and stir for 4 hours at room temperature in the dark to obtain a top coating; wherein the addition amount of 4-acryloxybenzophenone derivative 2 double network structure compound is 3% of the total mass of the top coating, the mass of polyethylene glycol diacrylate 1000 is 0.5% of the total mass of the top coating, and the mass of ethanol and deionized water is 96.5% of the total mass of the top coating.

[0060] (3) Dip the latex / silicone catheter into the base coating for 30 seconds, then irradiate with a UV lamp for 100 seconds, and then the base coating is cured on the latex / silicone catheter to form a base layer; then dip the latex / silicone catheter with the base layer into the top coating for 30 seconds, and irradiate with a UV lamp for 200 seconds. After the top coating is cured, a coated catheter is obtained.

[0061] Comparative Example 2

[0062] (1) Dissolve 4-acryloxybenzophenone derivative 1 and polyethylene glycol diacrylate 1000 in a mixed solvent of ethanol and deionized water, and stir for 2 hours at room temperature in the dark to obtain a primer; wherein the amount of 4-acryloxybenzophenone derivative 1 added is 3% of the total mass of the primer, the mass of polyethylene glycol diacrylate 1000 is 0.7% of the total mass of the primer, and the mass of ethanol and deionized water is 96.3% of the total mass of the primer.

[0063] (2) The double network structure compound of 4-acryloxybenzophenone derivative 2 is replaced with a hydrophilic polymer polyvinylpyrrolidone with a molecular weight of 1.3 million, and then polyvinylpyrrolidone and polyethylene glycol diacrylate 1000 are dissolved in a mixed solvent of ethanol and deionized water. After stirring for 4 hours at room temperature in the dark, benzophenone photoinitiator is added and stirring is continued for 30 minutes to obtain a top coating; wherein the amount of polyvinylpyrrolidone added is 3% of the total mass of the top coating, the mass of polyethylene glycol diacrylate 1000 is 0.5% of the total mass of the top coating, the mass of benzophenone is 6% of the mass of polyethylene glycol diacrylate, the mass of ethanol and deionized water is 96.5% of the total mass of the top coating, and the mass ratio of ethanol to deionized water is 9:1.

[0064] (3) Dip the latex / silicone catheter into the base coating for 30 seconds, then irradiate with a UV lamp for 100 seconds, and then the base coating is cured on the latex / silicone catheter to form a base layer; then dip the latex / silicone catheter with the base layer into the top coating for 30 seconds, and irradiate with a UV lamp for 200 seconds. After the top coating is cured, a coated catheter is obtained.

[0065] Performance test: The urinary catheters prepared in Examples 1-5, Comparative Example 1 and Comparative Example 2 were tested for super-slip performance and balloon toughness. The test results are shown in Table 1, which are as follows:

[0066] 1. Test methods for lubricity and durability of super-slip coatings

[0067] According to the standard test model for evaluation of sliding performance of non-intravascular catheter surface in YYT1536-2017, the friction coefficient of the coated and cured catheter samples was tested for 1000 test cycles.

[0068] 2. Integrity test method for the front balloon coating of the catheter

[0069] The coated and completely cured catheter was immersed in 1% Congo red dye solution and dyed for 1 minute. The catheter sample was then taken out and rinsed with deionized water to wash away the undyed Congo red dye solution. Then, 30 mL of pure water was injected into the main cavity of the catheter, and the coating on the balloon surface was directly observed with the naked eye after magnification of 2.5 times.

[0070] Table 1 Lubricity and durability test data of the super-slip coatings prepared in the examples and comparative examples

[0071]

[0072] Combining the data in Table 1 and the contents in the attached drawings, it can be seen that after the coating prepared by Comparative Example 1 was coated on the latex / silicone catheter, the friction coefficient showed a linear upward trend after 30 frictions. This shows that the lubricity and durability of the coating prepared by this comparative example are relatively poor; however, after the balloon at the front end of the catheter coated with the coating was inflated, the coating on the balloon remained intact without cracks; this shows that the toughness of the coating is good. After the coating prepared by Comparative Example 2 was coated on the latex / silicone catheter, after 1000 frictions, its friction coefficient was less than 0.04. Compared with the uncoated catheter sample, the friction coefficient decreased by about 99%. However, after the balloon at the front end of the catheter coated with the coating was inflated, the coating on the balloon was obviously broken; this shows that the toughness of the coating is relatively poor. After the latex / silicone catheter was coated with the high-toughness super-slip coating provided by the present invention, the friction coefficient decreased by 99.1%-99.9% compared with the uncoated blank balloon catheter, and after 1,000 frictions, the friction coefficient was stabilized between 0.01-0.04, which shows that the coating has excellent lubricity and durability. In addition, after the balloon at the front end of the catheter was inflated, the coating on the balloon remained intact without cracks, which shows that the coating has excellent toughness.

[0073] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A high-toughness ultra-slip coating, comprising a bottom layer and a surface layer, prepared by immersing a substrate in a bottom layer coating and a surface layer coating in sequence for a certain period of time, and then curing the substrate with ultraviolet light, characterized in that: The viscosity of the primer is 1.52mPa•S-3.72mPa•S, and the main raw materials are vinyl benzophenone derivative 1, reactive diluent and organic solvent, and the main raw materials of the vinyl benzophenone derivative 1 are vinyl acetate monomer, vinyl benzophenone monomer, thermal initiator and vinyl silane coupling agent monomer; The addition amounts of the vinyl benzophenone derivative 1, the reactive diluent and the organic solvent are 2%-5%, 0.7%-1.5% and 93.5%-97.3% of the total mass of the primer, respectively; The surface coating has a viscosity of 30.7 mPa•S-48.5 mPa•S, and is mainly made of a vinyl benzophenone derivative 2 double network structure compound, a reactive diluent and an organic solvent. The vinyl benzophenone derivative 2 double network structure compound is mainly made of acrylamide monomer, vinyl benzophenone monomer, a thermal initiator, a vinyl silane coupling agent monomer and polyvinyl pyrrolidone. The added amounts of the vinyl benzophenone derivative 2 double network structure compound, the active diluent and the organic solvent are 2%-5%, 0.5%-1.5% and 93.5%-97.5% of the total mass of the surface coating, respectively.

2. The high-toughness super-slip coating according to claim 1, characterized in that: The molar ratio of the vinyl acetate monomer, the vinyl benzophenone monomer, and the vinyl silane coupling agent monomer is (0.03-0.045):(0.25-0.75):(0.5-1); the content of the thermal initiator is 0.5%-2% of the total mass of each monomer.

3. The high-toughness super-slip coating according to claim 1, characterized in that: The molar ratio of the vinyl benzophenone monomer, the acrylamide monomer and the vinyl silane coupling agent monomer is (0.03-0.045):(0.5-1):(0.1-0.3); the content of the thermal initiator is 0.5%-2% of the total mass of each monomer; and the added amount of polyvinyl pyrrolidone is 50%-80% of the total mass of the solution.

4. A method for preparing a high-toughness ultra-slip coating according to any one of claims 1 to 3, characterized in that: The following steps are involved: Step A, preparation of vinyl benzophenone derivative 1: adding a certain molar mass of vinyl acetate monomer to a reaction vessel, adding anhydrous ethanol, vinyl benzophenone monomer, and a thermal initiator, heating and stirring under nitrogen protection, then dropping a vinyl silane coupling agent monomer, continuing to stir after heating, and stopping heating when the reaction is completed to prepare a vinyl benzophenone derivative 1; Step B, preparation of a double network structure compound of a vinyl benzophenone derivative 2: adding a certain molar mass of acrylamide monomer to a reaction container, adding anhydrous ethanol, vinyl benzophenone monomer, and a thermal initiator, heating and stirring under nitrogen protection, then dropping a vinyl silane coupling agent monomer, continuing to stir after heating, and simultaneously adding a certain mass of polyvinyl pyrrolidone ethanol solution, continuing to stir and react for a period of time, stopping heating after the reaction is completed, and preparing a double network structure compound of a vinyl benzophenone derivative 2; Step C, preparation of the base coating: dissolving the vinyl benzophenone derivative 1 prepared in step A and the active diluent in an organic solvent or water, stirring for 2 hours at room temperature in the dark, to obtain the base coating; Step D, preparation of the surface coating: dissolving the vinyl benzophenone derivative 2 double network structure compound prepared in step B and the active diluent in an organic solvent or water, stirring at room temperature in the dark for 4 hours, and obtaining the surface coating; Step E, preparation of high-toughness ultra-smooth coating: first, dip the substrate into the base coating, and form a base layer after soaking and UV curing; then dip the substrate with the base layer into the surface coating, and form a high-toughness ultra-smooth coating after soaking and UV curing.

5. The preparation method according to claim 4, characterized in that: The vinyl benzophenone monomer in step A and step B includes any one of 4-acryloxybenzophenone, 4-vinyloxybenzophenone, 4-acrylamidebenzophenone, 4-propyleneoxybenzophenone and 4-methacryloxybenzophenone.

6. The preparation method according to claim 4, characterized in that: The thermal initiator in step A and step B includes any one of azobisisobutyronitrile and benzoyl peroxide.

7. The preparation method according to claim 4, characterized in that: The vinyl silane coupling agent monomer in step A and step B includes any one of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (β-methoxyethoxy) silane and γ-methacryloxypropyl trimethoxy silane.

8. The preparation method according to claim 4, characterized in that: The active diluent in step C and step D includes any one or two of polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, furan acrylate and isobornyl acrylate.

9. The preparation method according to claim 4, characterized in that: The organic solvent in step C and step D includes any one or two of ethanol and isopropanol.

10. The preparation method according to claim 4, characterized in that: The number average molecular weight of the polyvinyl pyrrolidone in step B is in the range of 600,000 to 1.3 million.

11. The preparation method according to any one of claims 5 to 10, characterized in that: In step E, the substrate is dipped in the primer for 10s-60s, and the UV lamp irradiation time is 60s-120s; the substrate is dipped in the topcoat for 10s-60s, and the UV lamp irradiation time is 100s-240s.

12. The preparation method according to claim 11, characterized in that: In step E, the substrate includes any one of a latex catheter, a silicone catheter, a polyurethane catheter, and a polyvinyl chloride catheter.

13. A balloon catheter comprising the high-toughness super-slip coating according to any one of claims 1 to 3, characterized in that: Compared with the uncoated blank balloon catheter, the friction coefficient decreased by 99.1%-99.9%, and after 1000 frictions, its friction coefficient stabilized between 0.01-0.04; after the balloon at the front end of the catheter was inflated, the coating on the balloon remained intact without any cracks.

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