阅读说明：本技术 基于电子束固化的医疗器械表面亲水超滑涂层及制备方法 (Medical instrument surface hydrophilic ultra-smooth coating based on electron beam curing and preparation method thereof ) 是由 万美春 廖权昌 胡志林 白昌建 殷利明 万堡 于 2021-01-11 设计创作，主要内容包括：本发明公开了基于电子束固化的导尿管表面亲水超滑涂层及制备方法,涉及医疗材料技术领域,其技术方案要点是：该亲水超滑涂层以质量百分比计,其成分组成为N-乙烯基吡咯烷酮：60-90％、带有不饱和基团的多官能度化合物：1-10％、乙烯基吡咯烷酮的多种均聚物：0.5-3％、带有超滑效果的天然大分子物质：0.5-3％、不饱和基团封端的单官能度聚氧乙烯醚：1-5％、聚氨酯丙烯酸酯化合物：1-10％、带不饱和基团的有机聚硅氧烷：0.1％-2％、单官能度的丙烯酸酯小分子化合物：1-5％。本发明的亲水超滑涂层的无溶剂、无引发剂残留、能快速固化、不危害环境和操作人员；同时,本发明以电子束固化的方法将涂层固化于导尿管表面,便于在导尿管内外多维度表面实现稳定的亲水超滑效果。(The invention discloses a hydrophilic ultra-smooth coating on the surface of a catheter based on electron beam curing and a preparation method thereof, relating to the technical field of medical materials, and the key points of the technical scheme are as follows: the hydrophilic ultra-smooth coating comprises the following components in percentage by mass: 60-90%, polyfunctional compounds with unsaturated groups: 1-10%, various homopolymers of vinyl pyrrolidone: 0.5-3%, natural macromolecular substances with super-smooth effect: 0.5-3%, and unsaturated group-terminated monofunctional polyoxyethylene ether: 1-5%, urethane acrylate compound: 1-10%, organopolysiloxane with unsaturated groups: 0.1% -2%, acrylate small molecular compound with single functionality: 1 to 5 percent. The hydrophilic super-smooth coating is free of solvent and initiator residue, can be quickly cured, and does not harm the environment and operators; meanwhile, the coating is solidified on the surface of the catheter by an electron beam solidification method, so that a stable hydrophilic and super-smooth effect can be realized on the internal and external multi-dimensional surfaces of the catheter.)

1. The electron beam curing-based hydrophilic super-smooth coating on the surface of the medical instrument is characterized in that: the composition comprises the following components in percentage by mass: 60-90%, polyfunctional compounds with unsaturated groups: 1-10%, various homopolymers of vinyl pyrrolidone: 0.5-3%, natural macromolecular substances with super-smooth effect: 0.5-3%, and unsaturated group-terminated monofunctional polyoxyethylene ether: 1-5%, urethane acrylate compound: 1-10%, organopolysiloxane with unsaturated groups: 0.1% -2%, acrylate small molecular compound with single functionality: 1 to 5 percent.

2. The electron beam curing based hydrophilic ultra-smooth coating on the surface of the medical device according to claim 1, which is characterized in that: the multifunctional compound with unsaturated groups is divinylbenzene, 1, 3-butanediol diacrylate, tripropylene glycol diacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofuran acrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate or polyethylene glycol diacrylamide.

3. The electron beam curing based hydrophilic ultra-smooth coating on the surface of the medical device according to claim 1, which is characterized in that: the various homopolymers of vinylpyrrolidone are polyvinylpyrrolidone having a K value of 17, 30, 60, 80, 85 or 90, wherein the K value is a characteristic of the molecular weight of the polyvinylpyrrolidone.

4. The electron beam curing based hydrophilic ultra-smooth coating on the surface of the medical device according to claim 1, which is characterized in that: the natural macromolecular substance with the super-slip effect is sodium hyaluronate, chitosan, natural gelatin, chitosan or sodium alginate.

5. The electron beam curing based hydrophilic ultra-smooth coating on the surface of the medical device according to claim 1, which is characterized in that: the monofunctional polyoxyethylene ether terminated by the unsaturated group is polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate or prenyl polyoxyethylene ether or methallyl alcohol polyoxyethylene ether.

6. The method for preparing the hydrophilic and super-smooth coating on the surface of the medical device based on the electron beam curing of any one of the claims 1 to 5, which is characterized in that: the method specifically comprises the following steps:

s1, preparing a coating material, and calculating according to the mass percentage: putting 60% of N-vinyl pyrrolidone, 5% of 1, 3-butanediol diacrylate, 1% of polyvinylpyrrolidone with a K value of 30, 0.5% of hyaluronic acid, 1% of polyethylene glycol methyl ether acrylate, 3% of medical-grade waterborne polyurethane emulsion, 0.5% of organic silicon flatting agent, 0.5% of organic silicon wetting agent and 28.5% of water into a three-neck flask, and uniformly mixing until the N-vinyl pyrrolidone, the 1, 3-butanediol diacrylate and the polyvinyl pyrrolidone are completely dissolved to obtain a material mixture;

s2, filtering the material mixture, and filtering the material mixture in the step S1 by adopting a 2000-mesh filter screen;

s3, coating the coating in a dipping mode, dipping the medical instrument into the material mixture filtered in the step S2 for 30S, then taking out the medical instrument, drying the medical instrument for 1min in hot air at the temperature of 80 ℃, and pre-drying the water on the surface of the medical instrument dipped with the material mixture;

s4, curing the coating, namely, sending the medical instrument dipped with the material mixture in the step S3 into an electron beam irradiation chamber, irradiating the material mixture dipped on the surface of the medical instrument for 15S with 100KGy of energy, curing the material mixture into a hydrophilic super-smooth coating on the surface of the medical instrument to obtain the hydrophilic super-smooth medical instrument, and then packaging and sterilizing the hydrophilic super-smooth medical instrument.

7. The method for preparing the hydrophilic and super-smooth coating on the surface of the medical device based on the electron beam curing as claimed in claim 6, which is characterized in that: the medical apparatus is a catheter, a vascular catheter or a guide wire bracket.

Technical Field

The invention relates to the technical field of medical materials, in particular to a hydrophilic super-smooth coating on the surface of a medical instrument based on electron beam curing and a preparation method thereof.

Background

The functional coating is coated on the surface of the medical appliance, so that the medical appliance has the performances of hydrophilicity, lubrication, antibiosis, anticoagulation, tissue hyperplasia resistance and the like, and the important technical scheme for improving the efficacy of the medical appliance, relieving the discomfort of a patient, enhancing the treatment effect and reducing the infection rate is provided. With the progress of medical technology, a large number of puncture needles, guide wires, catheters, catheter sheaths, stents and balloons which have the functions of super-lubricity, antibiosis, anticoagulation, drug controlled release and the like and are subjected to surface modification by medical coatings are widely applied in clinic, and bring welfare to patients.

Among coated surface modified medical devices, the application of hydrophilic super-lubricious coatings is the most fundamental clinical application. Such as the insertion and the replacement of catheters, vascular catheters and guide wire stents, because of the existence of the hydrophilic lubricating coating on the surface, the friction between the surface and the vascular wall is reduced, the biocompatibility is improved, and the treatment is easier to operate by doctors. In clinical application, the pain of a patient is reduced sharply, and the risk of vessel wall damage is also greatly reduced. Therefore, the application of hydrophilic ultra-smooth coatings on the surface of medical devices has the most widespread clinical application.

The hydrophilic ultra-smooth coating which can meet the clinical application has the advantages of good adhesion with the surface of a medical instrument, difficult shedding and good biocompatibility; meanwhile, the wet friction coefficient is low, and the rubber can be recycled for multiple times and is wiping-resistant.

At present, most of the mainstream hydrophilic super-smooth coatings for medical instruments are hydrophilic lubricating polymers such as hyaluronic acid, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, chitosan, polyoxyethylene ether and the like, and polyurethane-based or acrylic-based polymers, and the hydrophilic lubricating polymers are anchored on the surface of the medical instrument under the action of thermal curing or UV curing to form the hydrophilic super-smooth coating. However, the above methods all have different defects, such as that the coating layer adopting the heat curing method usually contains a large amount of organic solvent, harms the environment and operators in the hot air drying process, consumes time and energy, and has low production efficiency; the coating adopting the UV curing method has the problems of initiator residue and incapability of curing the inner wall of the non-transparent catheter, and limits clinical application to a certain extent. Therefore, the development of the hydrophilic super-smooth medical coating which is free of solvent, rapid in curing, multi-surface curing and initiator residue has very important significance.

Therefore, the invention aims to provide a medical instrument surface hydrophilic ultra-smooth coating based on electron beam curing and a preparation method thereof, so as to solve the problems.

Disclosure of Invention

The invention aims to solve the technical problems mentioned in the background technology and provides an electron beam curing-based hydrophilic ultra-smooth coating on the surface of a medical instrument and a preparation method thereof, wherein the hydrophilic ultra-smooth coating has the advantages of no solvent, no initiator residue, quick curing, no harm to the environment and operators, and can realize a stable hydrophilic ultra-smooth effect on the internal and external multidimensional surfaces of the medical instrument by an electron beam curing method.

The technical purpose of the invention is realized by the following technical scheme: the electron beam curing-based hydrophilic super-smooth coating on the surface of the medical instrument comprises the following components in percentage by mass: 60-90%, polyfunctional compounds with unsaturated groups: 1-10%, various homopolymers of vinyl pyrrolidone: 0.5-3%, natural macromolecular substances with super-smooth effect: 0.5-3%, and unsaturated group-terminated monofunctional polyoxyethylene ether: 1-5%, urethane acrylate compound: 1-10%, organopolysiloxane with unsaturated groups: 0.1% -2%, acrylate small molecular compound with single functionality: 1 to 5 percent.

Further, the polyfunctional compound having an unsaturated group is divinylbenzene, 1, 3-butanediol diacrylate, tripropylene glycol diacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofuran acrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate or polyethylene glycol diacrylamide.

Further, the various homopolymers of vinylpyrrolidone are characterized by polyvinylpyrrolidone having a K value of 17, 30, 60, 80, 85, or 90, wherein the K value is a characterization of the molecular weight of the polyvinylpyrrolidone.

Further, the natural macromolecular substance with the super-slip effect is sodium hyaluronate, chitosan, natural gelatin, chitosan or sodium alginate.

Further, the monofunctional polyoxyethylene ether terminated by the unsaturated group is polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, isoamylene alcohol polyoxyethylene ether or methyl allyl alcohol polyoxyethylene ether.

The invention also provides a preparation method of the medical instrument surface hydrophilic ultra-smooth coating based on electron beam curing, which specifically comprises the following steps:

s1, preparing a coating material, and calculating according to the mass percentage: putting 60% of N-vinyl pyrrolidone, 5% of 1, 3-butanediol diacrylate, 1% of polyvinylpyrrolidone with a K value of 30, 0.5% of hyaluronic acid, 1% of polyethylene glycol methyl ether acrylate, 3% of medical-grade waterborne polyurethane emulsion, 0.5% of organic silicon flatting agent, 0.5% of organic silicon wetting agent and 28.5% of water into a three-neck flask, and uniformly mixing until the N-vinyl pyrrolidone, the 1, 3-butanediol diacrylate and the polyvinyl pyrrolidone are completely dissolved to obtain a material mixture;

s2, filtering the material mixture, and filtering the material mixture in the step S1 by adopting a 2000-mesh filter screen;

s3, coating the coating in a dipping mode, dipping the medical instrument into the material mixture filtered in the step S2 for 30S, then taking out the medical instrument, drying the medical instrument for 1min in hot air at the temperature of 80 ℃, and pre-drying the water on the surface of the medical instrument dipped with the material mixture;

s4, curing the coating, namely, sending the medical instrument dipped with the material mixture in the step S3 into an electron beam irradiation chamber, irradiating the material mixture dipped on the surface of the medical instrument for 15S with 100KGy of energy, curing the material mixture into a hydrophilic super-smooth coating on the surface of the medical instrument to obtain the hydrophilic super-smooth medical instrument, and then packaging and sterilizing the hydrophilic super-smooth medical instrument.

Further, the medical apparatus is a catheter, a vascular catheter or a guide wire stent and the like.

In conclusion, the invention has the following beneficial effects:

1. the hydrophilic super-slip coating on the surface of the medical instrument is coated and cured by an electron beam curing method, wherein the electron beam consists of a batch of accelerated electron flow, substances generate free radicals or ion radicals under the action of high-energy electron beams, and the free radicals or ion radicals are crosslinked with other substances to form a network polymer;

2. the N-vinyl pyrrolidone in the composition of the hydrophilic super-slip coating can be rapidly polymerized and cured under the action of electron beam rays, is the most main hydrophilic super-slip component in the coating, and can be used as an active diluent to facilitate dissolving other components and adjusting the viscosity of the coating; in addition, the multifunctional small molecular compound with unsaturated groups has the effects of improving the crosslinking density of the coating, reducing the water solubility of the coating and improving the durability; various homopolymers of vinyl pyrrolidone function to enhance the hydrophilic super-slip properties of the coating; the natural macromolecular substance with the super-lubricity effect can enhance the hydrophilic super-lubricity and biocompatibility of the coating; the polyoxyethylene ether with the end capped by the unsaturated group can adjust the crosslinking density in the composition and simultaneously generate a macromolecular comb-shaped chain segment, so that the hydrophilicity of the coating can be better improved; the hydrophilic super-smooth coating is convenient to realize the effects of no solvent, no initiator residue, quick curing and no harm to the environment and operators through each composition of the hydrophilic super-smooth coating.

Drawings

Fig. 1 is a flowchart in embodiment 2 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Aiming at the problems in the prior art, the invention provides a medical instrument surface hydrophilic ultra-smooth coating based on electron beam curing and a preparation method thereof, and the invention is described in detail below with reference to the accompanying drawings.

Example 1: the electron beam curing-based hydrophilic super-smooth coating on the surface of the medical instrument comprises the following components in percentage by mass: 60-90%, polyfunctional compounds with unsaturated groups: 1-10%, various homopolymers of vinyl pyrrolidone: 0.5-3%, natural macromolecular substances with super-smooth effect: 0.5-3%, and unsaturated group-terminated monofunctional polyoxyethylene ether: 1-5%, urethane acrylate compound: 1-10%, organopolysiloxane with unsaturated groups: 0.1% -2%, acrylate small molecular compound with single functionality: 1 to 5 percent.

In this example, N-vinylpyrrolidone, having the definite CAS registry number 88-12-0, rapidly polymerizes and cures under the action of electron beam radiation, and is the most predominant hydrophilic super-slip component in the coating; at the same time, it can act as a reactive diluent, dissolving other components and adjusting the viscosity of the coating.

Wherein the polyfunctional compound having an unsaturated group is divinylbenzene, 1, 3-butanediol diacrylate, tripropylene glycol diacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofuran acrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate or the like.

In this example, the polyfunctional small molecule compound having an unsaturated group functions to increase the crosslinking density of the coating layer, reduce the water solubility of the coating layer, and improve the durability.

Wherein the various homopolymers of vinylpyrrolidone are polyvinylpyrrolidone having a K value of 17, 30, 60, 80, 85 or 90, wherein the K value is a representation of the molecular weight of the polyvinylpyrrolidone.

In this example, various homopolymers of vinylpyrrolidone function to enhance the hydrophilic super-slip properties of the coating.

Wherein, the natural macromolecular substance with super-slippery effect adopts sodium hyaluronate, chitosan, natural gelatin, chitosan or sodium alginate, etc.

In this embodiment, the natural macromolecular substance with the super-slip effect functions to enhance the hydrophilic super-slip and biocompatibility of the coating.

Wherein, the monofunctional polyoxyethylene ether terminated by the unsaturated group adopts polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, isoamylol polyoxyethylene ether or methyl allyl alcohol polyoxyethylene ether and the like.

In the embodiment, the polyoxyethylene ether terminated by unsaturated groups has the function of adjusting the crosslinking density, and meanwhile, the polyoxyethylene ether can generate macromolecular comb-shaped chain segments, so that the hydrophilicity of the coating can be better improved.

Example 2: the invention also provides a preparation method of the medical instrument surface hydrophilic ultra-smooth coating based on electron beam curing, which specifically comprises the following steps as shown in figure 1:

s1, preparing a coating material, and calculating according to the mass percentage: putting 60% of N-vinyl pyrrolidone, 5% of 1, 3-butanediol diacrylate, 1% of polyvinylpyrrolidone with a K value of 30, 0.5% of hyaluronic acid, 1% of polyethylene glycol methyl ether acrylate, 3% of medical-grade waterborne polyurethane emulsion, 0.5% of organic silicon flatting agent, 0.5% of organic silicon wetting agent and 28.5% of water into a three-neck flask, and uniformly mixing until the N-vinyl pyrrolidone, the 1, 3-butanediol diacrylate and the polyvinyl pyrrolidone are completely dissolved to obtain a material mixture.

Wherein the molecular weight of the polyethylene glycol methyl ether acrylate is 2400.

S2, filtering the material mixture, and filtering the material mixture in the step S1 by adopting a 2000-mesh filter screen.

S3, coating the catheter in a dipping mode, dipping the catheter into the material mixture filtered in the step S2 for 30S, then taking out the catheter, drying the catheter in hot air at the temperature of 80 ℃ for 1min, and pre-drying moisture on the surface of the catheter dipped with the material mixture.

S4, curing the coating, namely conveying the catheter dipped with the material mixture in the step S3 into an electron beam irradiation chamber, irradiating the material mixture dipped on the surface of the catheter for 15S with 100KGy of energy, curing the material mixture into the hydrophilic super-smooth coating on the surface of the catheter to obtain the hydrophilic super-smooth catheter, and then packaging and sterilizing the hydrophilic super-smooth catheter.

After the hydrophilic ultra-smooth catheter prepared in the embodiment is soaked in water, the wet friction coefficient is less than 0.05, and the number of times of circulating friction is greater than 100.

The hydrophilic super-slip coating on the surface of the catheter is coated and cured by an electron beam curing method, the electron beam is composed of a batch of accelerated electron flow, substances generate free radicals or ion radicals under the action of high-energy electron beams, the free radicals or the ion radicals are then crosslinked with other substances to form a network polymer, compared with ultraviolet light UV, the particle energy of the electron beam is far higher than that of the ultraviolet light, air ionization can be realized, a photoinitiator is not needed in the electron beam curing, chemical reaction can be directly initiated, the penetrating power of the substances is strong, the inner and outer multi-dimensional surfaces of an irregular opaque part can be irradiated, the coating can be rapidly cured on the surface of the catheter, and the hydrophilic super-slip effect of the inner and outer multi-dimensional surfaces of the catheter is convenient to realize.

Meanwhile, the N-vinyl pyrrolidone in the hydrophilic super-slip coating can be rapidly polymerized and cured under the action of electron beam rays, is the main hydrophilic super-slip component in the coating, and can be used as an active diluent to facilitate dissolving other components and adjusting the viscosity of the coating. In addition, the polyfunctional small-molecular compound having an unsaturated group functions to increase the crosslinking density of the coating layer, and can reduce the water solubility of the coating layer and improve the durability. Various homopolymers of vinyl pyrrolidone function to enhance the hydrophilic super-slip properties of the coating. The natural macromolecular substance with the super-lubricity effect can enhance the hydrophilic super-lubricity and biocompatibility of the coating. The polyoxyethylene ether with the end capped by the unsaturated group can adjust the crosslinking density in the composition and simultaneously generate a macromolecular comb-shaped chain segment, thereby better improving the hydrophilicity of the coating. The hydrophilic super-smooth coating is convenient to realize the effects of no solvent, no initiator residue, quick curing and no harm to the environment and operators through each composition of the hydrophilic super-smooth coating.

The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.